CN101142868A - Light-transmitting electromagnetic shielding film, optical filter and plasma television - Google Patents

Light-transmitting electromagnetic shielding film, optical filter and plasma television Download PDF

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Publication number
CN101142868A
CN101142868A CNA2006800083192A CN200680008319A CN101142868A CN 101142868 A CN101142868 A CN 101142868A CN A2006800083192 A CNA2006800083192 A CN A2006800083192A CN 200680008319 A CN200680008319 A CN 200680008319A CN 101142868 A CN101142868 A CN 101142868A
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China
Prior art keywords
light
layer
film
transmitting electromagnetic
dyestuff
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Chinese (zh)
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佐佐木博友
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Fujifilm Corp
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Fujifilm Corp
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
    • C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/10—AC-PDPs with at least one main electrode being out of contact with the plasma
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20—Constructional details
    • H01J11/34—Vessels, containers or parts thereof, e.g. substrates
    • H01J11/44—Optical arrangements or shielding arrangements, e.g. filters, black matrices, light reflecting means or electromagnetic shielding means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0094—Shielding materials being light-transmitting, e.g. transparent, translucent
    • H05K9/0096—Shielding materials being light-transmitting, e.g. transparent, translucent for television displays, e.g. plasma display panel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2211/00—Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
    • H01J2211/20—Constructional details
    • H01J2211/34—Vessels, containers or parts thereof, e.g. substrates
    • H01J2211/44—Optical arrangements or shielding arrangements, e.g. filters or lenses
    • H01J2211/446—Electromagnetic shielding means; Antistatic means

Abstract

Disclosed is a light-transmitting electromagnetic shielding film which has both high electromagnetic shielding properties and high infrared blocking properties. Specifically disclosed is a light-transmitting electromagnetic shielding film wherein a metal silver portion and a light-transmitting portion are formed by exposing and developing an emulsion layer which is arranged on a supporting body and contains a silver salt emulsion. This light-transmitting electromagnetic shielding film is characterized by having infrared blocking properties.

Description

Light-transmitting electromagnetic screened film, filter and plasma display
Technical field
The present invention relates to the light-transmitting electromagnetic screened film, it can shield electromagnetic wave that produces from fronts such as display such as cathode ray tube (CRT), plasma display (PDP), LCD, electroluminescence (EL) display or Field Emission Display (EFD), microwave oven, electronic installation, printed substrates and filter and the plasma display that has light transmission and have this light-transmitting electromagnetic screened film.
Background technology
Along with the increase of the use of recent various electric equipments and electronic device, electromagnetic interference (EMI) sharply increases.Should point out that EMI not only causes mechanical breakdown and obstruction in the Electrical and Electronic device, and the staff's that operates these devices health is also had adverse effect.Therefore, need electromagnetic intensity that control produces from electric device/electronic device to be no more than standard or prescribed level.
As the countermeasure of pin with above-mentioned EMI, need shielding electromagnetic wave, the characteristic of obviously utilizing metal not allow electromagnetism to see through can realize this point.Therefore, for example, adopt the method for using the housing of making by metal or high conductive material, between circuit substrate, inserted the method for metallic plate and with the method for metal forming coating cable.Yet the display of CRT, PDP etc. should be transparent, because operating personnel should confirm character that shows on the screen etc.Yet in above-mentioned every kind of method, the front of display often becomes opaque, thereby makes these methods be not suitable as the electromagnetic wave shielding method.
Compare with CRT etc., PDP produces a large amount of electromagnetic waves.Therefore, require PDP to have stronger electromagnetic wave shielding performance.The electromagnetic wave shielding performance can be represented with surface resistivity simply.Its surface resistivity of light-transmitting electromagnetic shielding material that is used for CRT should be about 300 Ω/sq or littler, and its surface resistivity of light-transmitting electromagnetic shielding material that is used for PDP should be about 2.5 Ω/sq or littler.In addition, be used for the light-transmitting electromagnetic shielding material that plasma TV that the consumer uses uses and have high conductivity, be i.e. about 1.5 Ω of surface resistivity/sq or littler, preferred 0.1 Ω/sq or littler.
About transparency, its transparency of light-transmitting electromagnetic shielding material that is used for CRT should be about 70% or bigger, and its transparency of light-transmitting electromagnetic shielding material that is used for PDP is higher, is 80% or bigger.
For overcoming the problems referred to above, proposed to use wire netting to obtain the good electromagnetic wave shielding performance and the various materials and the method for the high grade of transparency with opening, will describe below.
(1) conductive fiber
For example, patent documentation 1 discloses a kind of electromagnetic shielding material of being made by conductive fiber.Yet the problem that this shielding material faces is to have the cross hatch width of broad, therefore, when being used to shield display screen, makes the screen deepening.Consequently, the character shown on the display almost can't be seen.
(2) by electroless process obtain netted
Propose a kind of method, comprised and use electroless plating catalyst printing grid pattern, carried out electroless plating (referring to for example, patent documentation 2 and patent documentation 3 etc.) then.Yet in this case, the catalyst of printing has the live width of broad, about 60 μ m, and this makes it needing be unsuitable for the display of relative narrower live width and precise pattern.
In addition, propose a kind of method, comprised that coating contains photoresist, exposure and the development of electroless plating catalyst, formed the electroless plating catalyst pattern, carried out electroless plating (referring to for example, patent documentation 4) then.Yet the visible light transmissivity of conducting film is 72%, therefore, so only can obtain inadequate transparency.In addition, the problem that this method faces is manufacturing cost, and the palladium that promptly needs to use high price is as electroless plating catalyst, to remove the major part exposure portion after the exposure.
(3) use photolithography by etching method obtain netted
Proposed a kind of method, wherein used photolithography on transparent base, to form metal net shaped film (referring to for example, patent documentation 5 is to patent documentation 8 etc.) by etching method.Owing to can carry out little processing, thereby the advantage of this method is that formation has the netted of high aperture (high permeability) and can shield stronger electromagnetism release.On the other hand, its problem that faces is, manufacture process trouble and complicated, therefore, the cost height.In addition, be known that owing to the use etching process, thereby the problem of grid pattern is that the live width of intersection point is wideer than straight line.In addition, point out that this method faces the problem that should overcome ripple.
(4) use silver halide by copper facing on conducting metal silver and developed silver obtain netted
Proposed to use the netted method of conducting metal silver formation conduction that obtains through silver halide is developed, or by form the netted method of conduction (referring to for example, patent documentation 9 and patent documentation 10) with metallic copper plating netted developed silver through silver halide being developed obtain.
In order for example to prevent that in the fault aspect the Long-distance Control, near infrared ray-cut-out function is considered to electromagnetic shielding film and the needed key factor of PDP as mentioned above, such as in patent documentation 11 and patent documentation 12 report.
Patent documentation 1:JP-A-5-327274
Patent documentation 2:JP-A-11-170420
Patent documentation 3:JP-A-5-283889
Patent documentation 4:JP-A-11-170421
Patent documentation 5:JP-A-2003-46293
Patent documentation 6:JP-A-2003-23290
Patent documentation 7:JP-A-5-16281
Patent documentation 8:JP-A-10-338848
Patent documentation 9:JP-A-2004-207001
Patent documentation 10:JP-A-2004-221564
Patent documentation 11:JP-A-9-247581
Patent documentation 12:JP-A-10-75087
Summary of the invention
The problem to be solved in the present invention
With compare by using the photoetching process etching to prepare netted method, the wire netting that obtains by the silver halide photography art of using silver halide is favourable as mentioned above, because it can be with lower production cost by the preparation of the step of less amount, and display light scattering and have low mist degree hardly in addition.
On the other hand, along with the nearest improvement of PDP brightness, produce the near infrared ray of recruitment.
Therefore, need to improve near infrared ray and cut off function.
In addition, in the above in the patent documentation disclosed method run into following problem.
(in the electroless process low productivity ratio)
For example, the transparency conducting film for preparing by the sensitive photographic material that uses disclosed silver salt in patent documentation 10 can accurately form thread pattern, realizes that therefore aspects such as high light transmittance, the low-cost mass preparation of permission are favourable.But because the silver-colored netting gear that develops has high resistance, the film that so obtains may be difficult to stand direct metallide.Have in the situation of large-area this film in plating, therefore all need to use electroless plating and metallide.But, when electroless plating and metallide use together, cause that for example productivity ratio reduces and the problem of electroplating cost increase.
When comprising that by use sheet feed system by patent documentation 10 disclosed technology carries out metallide in batches, the problem that often causes is, in surface resistivity is in 1 Ω/ or the higher film, is higher than and the electroplating solution contact portion by near the zone plating degree the electric current side.This phenomenon is electroplating beginning, and is obvious especially when promptly switching on for the first time, also is difficult to form uniform coating even make to continue then to electroplate.Along with surface resistivity increases, this problem becomes more serious.
(poor efficiency that causes by discontinuous netted pattern)
Except by the patent documentation 1 disclosed fiber process, the method netted by current obtainable formation all can not form continuous 3m of single pattern or longer net.For example, in the method for using silk screen printing, form net-like pattern by the pattern of repeating print with the half tone size.As a result, the pattern of gained interrupts in each half tone size unit or the formation lap.That is to say that this method forms node and also do not make under the continuity fracture and can not be completed into printed patterns neither making.In photoetching process, netted by each exposed mask size unit interruption.That is, the pattern that is formed by photoetching process has no net-like pattern part.This is because use sheet type photomask to expose, the photoresist of the volume form membrane that therefore can not all expose long continuously and repeat exposure in corresponding to the zone of photomask size inevitably.
In order to be used for PDP, for example convention is to use wherein with PDP module or front plate or has the preparation method of the net-like pattern of the shielding material that the filter location of the base material of being made by glass etc. makes up.This method causes the remarkable loss of shielding material.In addition, when the shielding material that plan to use connects and be curled into roller improved productivity ratio, speed of production also can not be improved fully in the long-time location of cost therefore.
For example cut off function by give near infrared ray to electromagnetic shielding film adhesive function layer.As long as the electromagnetic shielding film by using interrupt status as mentioned above and cause that remarkable loss makes filter, having that film that near infrared ray cuts off function also runs into only is effective shortcoming in interrupt status.
That has finished in these cases an object of the present invention is to solve above-mentioned problem about the electromagnetic shielding film performance improvement.More particularly, the object of the invention is to provide a kind of light-transmitting electromagnetic screened film with continuous net-shaped pattern with high productivity ratio and low price making under the shielding material loss minimum, its aspect durability be excellent, have high electromagnetic wave shielding character, a display light scattering and have high light transmittance hardly.
Another object of the present invention provides a kind of light-transmitting electromagnetic screened film of realizing the near infrared ray cut-out function of excellent electromagnetic wave shielding character and excellence simultaneously.
A further object of the present invention is filter and the plasma display by using this light-transmitting electromagnetic screened film to provide excellent electromagnetic wave shielding character of realization simultaneously and excellent near infrared ray to cut off function.
The method of dealing with problems
Solved aforesaid problem by following invention.
(1) a kind of light-transmitting electromagnetic screened film, it has argent part and light transmission part, and these parts are formed at the emulsus liquid layer that comprises silver salt emulsion on the support by exposure, and developing then forms, and
Wherein said light-transmitting electromagnetic screened film has infrared shield character.
(2) the light-transmitting electromagnetic screened film described in top (1), it comprises the infrared ray absorbing dyestuff in support.
(3) the light-transmitting electromagnetic screened film described in top (1) comprises the infrared ray absorbing dyestuff in its layer on being formed at support.
(4) the light-transmitting electromagnetic screened film described in top (3), its with metallic silver portion divide opposition side be formed on the support the layer in comprise the infrared ray absorbing dyestuff.
(5) the light-transmitting electromagnetic screened film described in top (3), its with metallic silver portion branch same side be formed on the support the layer in comprise the infrared ray absorbing dyestuff.
(6) the light-transmitting electromagnetic screened film described in top (1), it has adhesive layer and comprise the infrared ray absorbing dyestuff in described adhesive layer.
(7) as the light-transmitting electromagnetic screened film of top (1)-(6) described in any one, it has the conducting metal part that contains conducting metal in argent part, described conducting metal part is by using physical development to described metallic silver portion branch and/or electroplating process forms.
(8) the light-transmitting electromagnetic screened film described in top (7),
Wherein said conducting metal part forms by 1 μ m-40 μ m size that netted fine rule is formed and the continuous 3m of described net-like pattern or longer.
(9) as the light-transmitting electromagnetic screened film of top (1)-(8) described in any one,
Wherein carry out described exposure by the support that when carrying support, has an emulsus liquid layer that comprises silver salt emulsion with the light beam scan exposure.
(10) as the light-transmitting electromagnetic screened film of top (1)-(9) described in any one,
Wherein the silver-colored netting gear that obtains by the described emulsus liquid layer of developing the surface resistivity of 1-1000 Ω/ is arranged and under the transporting velocity at 1-30m/min after the development treatment by metallide continuously.
(11) as the light-transmitting electromagnetic screened film of top (3)-(10) described in any one,
The wherein said layer that comprises the layer of infrared ray absorbing dyestuff or contact with the described layer that comprises the infrared ray absorbing dyestuff comprises the antistatic agent that contains inorganic oxide.
(12) a kind of filter, it comprises as the light-transmitting electromagnetic screened film of top (1)-(11) described in any one.
(13) a kind of plasma display, its comprise as the light-transmitting electromagnetic screened film of top (1)-(11) described in any one or as top (12) described in filter.
Advantage of the present invention
According to the present invention, a kind of light-transmitting electromagnetic screened film can be provided, it is being excellent aspect durability, conductivity and the light transmitting property, hardly display light scattering and realized excellent electromagnetic wave shielding performance simultaneously and excellent near infrared ray cuts off function.The present invention also provides a kind of netted aforesaid light-transmitting electromagnetic screened film with continuous net-shaped pattern that comprises.
By using this light-transmitting electromagnetic screened film, filter and plasma display that the present invention can also provide a kind of near infrared ray that has excellent electromagnetic wave shielding character and excellence simultaneously to cut off function.
In addition, according to the present invention, can provide these products large-scale low-cost and can not cause the loss of production.
Description of drawings
Fig. 1 is the schematic diagram that shows an example of the metallide groove that can suitably be used for metallide process of the present invention.
Description of reference numerals
10 metallide grooves
11 plating bath
12a, the 12b feed roller
13 positive plates
14 deflector rolls
15 plating baths
16 films
17 draining rollers
Embodiment
The term of Shi Yonging " electromagnetic shielding film " expression herein comprises the membranaceous support with electromagnetic shielding film and the film of at least one other functional membrane.In some cases, " electromagnetic shielding film " only is called " film ".
The laminate that will comprise Plasma Display parts such as filter or contain its glass base-material is called " electromagnetic wave shielding compound ".
Term " netted " in " continuous net-shaped pattern " used herein means based on mode as known in the art, network pattern of being made up of many fine rules or the network of being made up of many fine rules.Term " continuous " means the film that long film for example curls, and wherein forms single pattern continuously on the length direction of described long film and does not interrupt.Their advantage hereinafter will be discussed.
Light-transmitting electromagnetic screened film according to the present invention is wherein to be formed at the emulsus liquid layer that comprises silver salt emulsion on the support by exposure, developing then forms argent part and light transmission part, and is characterised in that the light-transmitting electromagnetic screened film with shielding infrared ray character.
[formation of light-transmitting electromagnetic screened film]
In light-transmitting electromagnetic screened film according to the present invention, the thickness of support is preferably 5-200 μ m, more preferably 30-150 μ m.As long as the thickness of support drops in the scope of 5-200 μ m, can obtain required visible light transmittance rate and can easily handle film.
Can suitably determine to use the thickness of the argent part that on support, forms before physical development and/or the electroplating process according to the coating thickness that contains the silver salt coating on support to be coated.The thickness of argent part is preferably 30 μ m or lower, more preferably 20 μ m or lower, more preferably 0.01-9 μ m and most preferably 0.05-5 μ m.The argent of patterning partly is preferred.The laminate structures that the argent part can have single layer structure or have two-layer or multilayer.Argent partly be patterning and be to have in the situation of laminate structures of two-layer or multilayer, can give its different color photonasty, thus can be by sensitizing under various wavelength.By under various wavelength, exposing, can form patterns different from the layer to the layer.
In the situation that electromagnetic shielding film is used for display, the conducting metal part preferably has the visual angle that as far as possible little thickness increases display.In the situation of using the conductive connection material, need thinner film to realize higher density.Put from these, the conductive metal layer that loads on the described conducting metal part preferably has less than 9 μ m, but but more preferably 0.1 μ m or bigger less than 5 μ m and preferred again 0.1 μ m or bigger thickness less than 3 μ m.
In the present invention, because the coating thickness by control argentiferous salt deposit can form the metallic silver layer of desired thickness and can control the conducting metal particles layer arbitrarily by physical development and/or electroplating process, so even can easily form thickness less than 5 μ m, preferably less than the light-transmitting electromagnetic screened film of 3 μ m.
Opposite with the known engraving method that wherein must etch away and abandon most of metallic film, the present invention can only form the conducting metal pattern that comprises aequum on support, can only use the metal of required minimum, thereby obtain the advantage that production cost reduces and abandon the amount minimizing of metal.
[preparation method of light-transmitting electromagnetic screened film]
Light-transmitting electromagnetic screened film according to the present invention can prepare by the following method: by making the photosensitive material exposure that has the emulsion layer that contains silver halide on support, carry out developing process then, form argent part and light transmission part at exposure region and unexposed area respectively, if desired, the metallic silver portion branch is applied physical development and/or electroplating process, thereby make argent partly have conducting metal.
The method that forms light-transmitting electromagnetic conducting film of the present invention comprises following two kinds of patterns according to the photosensitive material and the developing process that use.
(I) make the Photoactive silver-halide monochromatism luminescent material that does not contain physical development nuclei accept chemical development or heat demonstration, thereby on described photosensitive material, form the pattern of argent part.
(II) thus making the Photoactive silver-halide monochromatism luminescent material that comprises physical development nuclei in the silver halide emulsus liquid layer accept the dissolving physical development forms argent pattern partly on described photosensitive material.
In above-mentioned integrated monochromatic developable embodiment (I), on photosensitive material, form argent.So the silver of the development that obtains is the silver or the heat-developed silver of chemical development with filament form of bigger serface.Therefore, in the physical development process, follow-up plating is a high activity.
In embodiment (II), silver halide particle dissolves near physical development nuclei and is deposited on the physical development nuclei in the exposure area.Therefore, on photosensitive material, form argent.This pattern also falls into integrated monochromatic developable classification.Although developing process causes that therefore deposition has also realized high activity on physical development nuclei, the silver that develops is the sphere with little surface area.
These patterns separately in, can select minus to develop or discharged-area development
The term of Shi Yonging " chemical development ", " heat development " and " dissolving physical development " herein has the meaning commonly used in this area.At the photochemistry document that generally uses, ShashinKagaku for example, Shinichi Kikuchi (Kyoritsu Shuppan, 1955) and The Theory ofPhotographic Processes, the 4th edition, C.E.K.Mees compiles in (Mcmillan, 1977) and has described these terms.Although this paper uses liquid handling, thermal development system also can be used as toning system in other is used.That is, purposes can comprise for example JP-A-2004-184693, JP-A-2004-334077, JP-A-2005-010752, Japanese patent application 2004-244080 and Japanese patent application 2004-085655.
(1) photosensitive material
(1-1) support
As the support of the photosensitive material that is used for preparation in accordance with the present invention, can use plastic film, plastic plate, glass plate etc.
As the material of aforesaid plastic film and plastic plate, can use for example polyethers such as PETG (PET) and poly-to (ethylene naphthalate); Polyolefin such as polyethylene (PE), polypropylene (PP), polystyrene and EVA; Vinyl base resin such as polyvinyl chloride and Vingon; Polyether-ether-ketone (PEEK), polysulfones (PSF), polyether sulfone (PES), Merlon (PC), polyamide, polyimides, acrylic resin, triacetyl cellulose (TAC) etc.
In the present invention, from transparency, thermal endurance, easily property handled and cost aspect, preferred aforesaid plastic film is PETG film or triacetyl cellulose (TAC) film.
Because it should be transparent being used for the electromagnetic shielding film of display, so preferred support has high transparency.In the case, total visible light transmittance rate of plastic film or plastic plate is preferably 70-100%, more preferably 85-100% and preferred especially 90-100%.In the present invention, can also use painted but its degree can not disturb plastic film or the plastic plate of realizing the object of the invention.
That be used for the present invention's plastic film or plastic plate and can be individual layer or comprise the two-layer or more multi-layered multilayer that combines.
Use in the present invention in the situation of glass plate as support, the kind of glass is not particularly limited.Be used for the situation of display at electromagnetic shielding film, preferred use provides the hard glass of hardened layer from the teeth outwards.Compare with non-hard glass, hard glass can prevent to break.From the viewpoint of fail safe, the hard glass that obtains by the air cooling method is preferred, because when fragmentation, it is broken into the small pieces that do not have sharp edges.
The thickness of support is 200 μ m or littler preferably, more preferably 20 μ m or bigger but be not more than 180 μ m and 50 μ m or bigger but be not more than 120 μ m most preferably.
(1-2) protective layer
Photosensitive material used herein can have the protective layer that is formed on the aftermentioned emulsus liquid layer.Term used herein " protective layer " means following layer, its by binding agent as or gelatin or high molecular polymer constitute and be formed on the sensitization emulsus liquid layer, thereby give anti-scratch effect and improve mechanical performance.Consider electroplating processes, also do not make its thickness minimum if preferably do not form protective layer or form.The preferred 0.2 μ m or littler of the thickness of protective layer.Can form protective layer by any known coating process, without limits.
(1-3) emulsus liquid layer
The photosensitive material that is preferred for preparing according to light-transmitting electromagnetic screened film of the present invention has emulsus liquid layer (layer that contains silver salt) on support.Emulsus liquid layer among the present invention can also randomly comprise dyestuff, binding agent, solvent etc. except silver salt.
＜dyestuff 〉
Photosensitive material can comprise dyestuff at least in the emulsus liquid layer.In the emulsus liquid layer, add dyestuff for various purposes, promptly as filter dye, be used to prevent the irradiation etc.As dyestuff, can comprise solid disperse dye.The example that preferably can be used for the dyestuff among the present invention comprises by as the general formula (FA) put down in writing among the JP-A-9-179243, (FA1), (FA2) and (FA3) dyestuff of representative.More particularly, the compound F 17-hydroxy-corticosterone 1-F34 that preferably in this patent documentation, quotes.In addition, can preferably use by the dyestuff (II-2)-(II-24) of JP-A-7-152112 report, by the dyestuff (III-5)-(III-18) of JP-A-7-152112 report, by the dyestuff (IV-2)-(IV-7) of JP-A-7-152112 report etc.
As other example that can be used for the dyestuff among the present invention, the solid dye that the fine solid particles form of being bleached in development or fixing is arranged that can exemplify is as cyanine dyes, pyrylium dye and the amine dyestuff by the JP-A-3-138640 report.The example of the dyestuff of not bleached in processing comprises the cyanine dyes with carboxyl by the JP-A-9-96891 report, the cyanine dyes that does not have acid groups by the JP-A-8-245902 report, color lake type cyanine dyes by the JP-A-8-333519 report, cyanine dyes by the JP-A-1-266536 report, emptying aperture type cyanine dyes by the JP-A-3-136038 report, pyrylium dye by the JP-A-62-299959 report, polymer-type cyanine dyes by the JP-A-7-253639 report, oxonol dyestuff by the fine solid particles dispersion of JP-A-2-282244 report, optical scatter by the JP-A-63-131135 report, Yb3+ compound by the JP-A-9-5913 report, by the ito powder of JP-A-7-113072 report etc.In addition, can also use by the general formula (F1) of JP-A-9-179243 report and the dyestuff of (F2) representing, the compound F 17-hydroxy-corticosterone 35-F112 that more specifically says so and in this patent documentation, quote.
Aforesaid dyestuff comprises water-soluble dye.The example of these water-soluble dyes comprises oxonol dyestuff, benzal dyestuff, melocyanine dyestuff, cyanine dyes and azo dyes.Wherein, oxonol dyestuff, hemioxonol dyestuff and benzal dyestuff are particularly useful in the present invention.The instantiation that can be used for water-soluble dye of the present invention comprises by British patent 584,609, the same 1,177,429, JP-A-48-85130, JP-A-49-99620, JP-A-49-114420, JP-A-52-20822, JP-A-59-154439, JP-A-59-208548, United States Patent (USP) 2,274,782, the same 2,533,472, the same 2,956,879, the same 3,148,187, the same 3,177,078, the same 3,247,127, the same 3,540,887, the same 3,575,704, the same 3,653,905 and the same 3, those dyestuffs of report in 718,427.
From the effect that prevents to shine with because of content increases the viewpoint that photosensitivity is descended, the content of the dyestuff in the emulsus liquid layer is based in the total solid matters scope that is selected in 0.01-10 weight % of fine quality, more preferably 0.1-5 weight %.
＜silver salt 〉
As the silver salt that uses in the present invention, what can exemplify has an inorganic silver salt, as silver halide.Preferred in the present invention the use has the silver halide of excellent specific property as photosensitive material.
Below, the silver halide that the present invention preferably uses is described.
The preferred in the present invention silver halide that plays the photosensitive material effect that uses.Therefore, also be applicable to the present invention about being used in silver halide optical thin film, photographic paper, plate-making film, photomask with the silver halide technology in emulsion mask etc.
Contained halogen element can be any in chlorine, bromine, iodine and the fluorine in the above-mentioned silver halide.In addition, can use the combination of these elements.For example, the preferred silver halide that uses comprises that AgCl, AgBr or AgI are as main component.More preferably the silver halide of Shi Yonging comprises that AgBr or AgI are as main component.Also preferably use the mixture of silver chlorate and silver bromide, the mixture of silver iodide, silver chlorate and silver bromide, or the mixture of silver iodide and silver bromide.More preferably use the mixture of silver chlorate and silver bromide, silver bromide, the mixture of silver iodide, silver chlorate and silver bromide, or the mixture of silver iodide and silver bromide.Most preferably use silver chlorate and the mixture of silver bromide or the mixture of silver iodide, silver chlorate and silver bromide that contains 50 moles of % or more silver chlorates.
In this specification, statement " containing the silver halide of AgBr (silver bromide) as main component " refers to that the mol ratio of bromide ion in the silver halide composition reaches 50% or bigger silver halide.Except bromide ion, contain AgBr and can contain bromide ion and chloride ion as the silver halide particle of main component.
Silver halide is a solid particulate form.Consider the picture quality in the pattern metal silver layer that forms after exposure and the development treatment, preferably the average grain diameter of the silver halide of representing with the diameter of corresponding ball is 0.1-1000nm (1 μ m), more preferably 0.1-100nm, more preferably 1-50nm again.
" diameter of corresponding ball " of term silver halide particle refers to have the diameter of the spheric granules of equal volume.
The content of the silver salt that comprises in the emulsus liquid layer is preferably 0.1-80 weight %, more preferably 1-50 weight %, and more preferably 3-30 weight %.
Silver halide particle is not particularly limited at vpg connection.That is, they can be that different shape is as sphere, cube, sheet shape (hexagon sheet, triangular piece, square sheets etc.), octangle, 14-face body or the like.Cube and 14-face body are preferred.
Silver halide particle can constitute by inside with as homogeneous surface.Selectively, it can have the different partial layer of halogen composition as inner or surperficial.
The silver halide emulsus liquid that is used as coating solution in emulsus liquid layer of the present invention can use and for example be documented in G.Glafkides, Chimie et Physique Photographique (PaulMontel, 1997), G.F.Dufin, Photographic Emulsion Chemistry (TheForcal Press, 1966), people such as V.L.Zelikman, method preparation among the Making and CoatingPhotographic Emulsion (The Forcal Press, 1964) etc.
As the method for the above-mentioned silver halide emulsus liquid of preparation, can use acid process or neutral method.As the method that makes the reaction of soluble silver salt and solubility haloid, can use one-sided mixed method, mixed method or its combination simultaneously.
In order to form silver-colored particle, can also use the method (that is so-called contrary mixed method) that in the presence of excessive silver ion, forms particle.In addition, as one of while mixed method, can use pAg wherein in being used to form the liquid phase of silver halide, to keep the method for constant level, the two injection methods of promptly so-called control.
Further preferably use so-called ag halide solvent such as ammoniacal liquor, thioether or quaternary thiocarbamide to form particle.In these methods, especially preferably use the quaternary thiourea compound of in JP-A-53-82408 and JP-A-55-77737, putting down in writing.The preferred example of quaternary thiourea compound comprises tetramethyl thiourea and 1,3-dimethyl-2-imidazolidinethione.Change although the addition of ag halide solvent is formed with the kind of compound used therefor, required particle diameter and halogen, be preferably 10 -5-10 -2The mol/mol silver halide.
By using the two injection methods of above-mentioned control or utilizing ag halide solvent to form the method for particle, the silver halide emulsus liquid that can easily obtain having regular crystal formation and narrower particle size distribution.Therefore, these methods are preferred among the present invention.
In order to make particle diameter even, preferably make silver by making growth fast in being no more than the scope of critical saturation with the following method: in British patent 1,535,016, the method for putting down in writing among JP-B-48-36890 and the JP-B-52-16354 according to germination rapid change nitrogenize silver or alkali halide adding speed, or in British patent 4,242,445 and JP-A-55-158124 in the method for the change concentration of aqueous solution put down in writing.Form the preferably monodispersed emulsion of silver halide emulsus liquid used in the emulsus liquid layer of the present invention, preferably the variation coefficient of { (standard deviation of particle diameter)/(average grain diameter) } * 100 representative is 20% or littler, more preferably 15% or littler, most preferably 10% or littler.
The silver halide emulsus liquid that uses among the present invention can be the mixture with multiple silver halide emulsus liquid of different-grain diameter.
The silver halide emulsus liquid that uses among the present invention can contain the metal that belongs to VII or VIIB family.For obtaining high contrast and low haze, particularly preferably be and contain rhodium compound, iridic compound, ruthenium compound, iron compound, osmium compound etc.These compounds can have various parts.The example of part comprises cyanide ion, halide ion, thiocyanate ion, nitrosyl ion, water, hydroxyl etc.Except these pseudohalogens and ammoniacal liquor, can also use organic molecule such as amine (methyl amine, ethylenediamine etc.), heterocyclic compound (imidazoles, thiazole, 5-methylthiazol, mercaptoimidazole etc.), urea and thiocarbamide.
In order to improve photosensitivity, advantageously use metal six cyano complex dopants, as K 4[Fe (CN) 6], K 4[Ru (CN) 6] or K 3[Cr (CN) 6].
As aforesaid rhodium compound, can use water miscible rhodium compound among the present invention.The example of water miscible rhodium compound comprises that halogenation rhodium (III), chlordene rhodium (III) complex salts, pentachloro-acor rhodium complex salt (pentachloro acorhodium complex salt), tetrachloro diagno rhodium complex salt (tetrachloro diagnorhodium complex salt), hexabromo rhodium (III) complex salts, hexamine rhodium (III) complex salts, three oxalic acid close rhodium (III) complex salts and K 3Rh 2Br 9
Use this rhodium compound by dissolving in water or suitable solvent.Can also use the solution of common method, promptly add the method for the hydrogen halides (example hydrochloric acid, hydrobromic acid or hydrofluoric acid) or alkali halide (as KCl, NaCl, KBr or the NaBr) aqueous solution with stabilizing rhodium compound.What replace use water-soluble rhodium compound is when the preparation silver halide, can also add and dissolve other silver halide particle that mixes with rhodium.
The example of above-mentioned iridic compound comprises chlordene iridium complex salt such as K 2IrCl 6Or K 3IrCl 6, hexabromo iridium complex salt, hexamine iridium complex salt and pentachloro-nitrosyl (nitrisil) iridium complex salt.
The example of above-mentioned ruthenium compound comprises chlordene ruthenium, pentachloro-nitrosyl ruthenium and K 4[Ru (CN) 6].
The example of above-mentioned iron compound comprises that six cyanogen close sour potassium of iron (II) and ferrous rhodanate.
Described in JP-A-63-2042, JP-A-1-285941, JP-A-2-20852 and JP-A-2-20855, add ruthenium or osmium with the water soluble complex salt form.As particularly preferred example, can quote 6-co-ordination complex by following general formula representative:
[ML 6] -n
Wherein M represents Ru or Os; And n represents 0,1,2,3 or 4.
In this case, counter ion is unimportant, for example can be the ammonium of alkali metal ion.In addition, the preferred example of part comprises halide part, cyanide part, oxycyanide part, nitrosyl radical part and sulfo-nitrosyl radical part.Next, the object lesson of the used complex compound of the present invention is shown, but the invention is not restricted to these examples.
[RuCl 6] -3、[RuCl 4(H 2O) 2] -1、[RuCl 5(NO)] -2、[RuBr 5(NS)] -2、
[Ru(CO) 3Cl 3] -2、[Ru(CO)Cl 5] -2、[Ru(CO)Br 5] -2、[OsCl 6] -3、[OsCl 5(NO)] -2、
[Os (NO) (CN) 5] -2, [Os (NS) Br 5] -2, [Os (CN 6)] -4[Os (O) 2(CN) 5] -4
The preferred addition of described compound is every mole of silver halide 10 -10-10 -2Mol/mol.Ag, more preferably 10 -9-10 -3Mol/mol.Ag.
Further preferably, use the silver halide that contains Pd (II) ion and/or Pd metal in the present invention.Pd can be evenly distributed in the silver halide particle, but preferably is contained near the superficial layer of silver halide particle.Term Pd " is included near the superficial layer of silver halide particle " and is meant that silver halide particle has the palladium content layer higher than other layer, and this layer is apart from the degree of depth 50nm on silver halide particle surface.
Can prepare this silver halide particle by in forming the process of silver halide particle, adding Pd, preferably after adding the silver ion that surpasses total addition 50% and halide ion, add Pd.Further preferably by in the post curing stage, adding Pd (II) ion, Pd (II) ion is present in the superficial layer of silver halide.
The silver halide particle of this Pd of containing has increased physical development or electroless speed, thereby has improved the manufacturing efficient of required electromagnetic shielding material.Consequently, help to reduce manufacturing cost.Pd is well-known, and as electroless catalyst, in the present invention, can make the Pd localization in the superficial layer of silver halide particle, thereby save extremely expensive Pd.
In the present invention, with respect to the molal quantity of the silver in the silver halide, Pd ion in silver halide and/or Pd metal preferred content are 10 -4-0.5mole/mol.Ag, more preferably 0.01-0.3mole/mol.Ag.
The Pd examples for compounds of using comprises PdCl 4And Na 2PdCl 4
In the present invention, can carry out the chemical sensitization in photograph emulsion, implemented, thereby further improve photosensitivity as photosensitive material.As chemical sensitization, can use chalcogen sensitizing such as sulphur sensitizing, selenium sensitizing or tellurium sensitizing, noble metal sensitizing such as golden sensitizing, or reduction sensitization.Described sensitizing can be used singly or in combination.Under the situation of the combination of the chemical sensitization of stating in the use, for example, the combination of sulphur sensitizing and golden sensitizing, the combination of sulphur sensitizing, selenium sensitizing and golden sensitizing, or the combination of sulphur sensitizing, tellurium sensitizing and golden sensitizing is preferred.
Usually by adding the sulphur sensitizer and under the high temperature more than 40 ℃, stirring the emulsion certain hour and carry out sulphur sensitizing.As the sulphur sensitizer, can use known sulphur compound, for example, contained sulphur compound or various sulphur compound such as thiosulfate, thiocarbamide, thiazole or rhodanine in the gelatin.Preferred sulphur compound is thiosulfate or thiourea compound.The addition of sulphur sensitizer during with chemical slaking for example pH and the various conditions such as particle diameter of temperature, silver halide change, and be preferably 10 -7-10 -2The mol/mol silver halide, more preferably 10 -5-10 -3Mol.
Selenium sensitizer as using in the selenium sensitizing can use known selenium compound.Usually by adding unsettled and/or non-unsettled selenium compound and under the high temperature more than 40 ℃, stirring the emulsion certain hour and carry out selenium sensitizing.As unsettled selenium compound, can use those that in JP-B-44-15748, JP-B-43-13489, JP-A-4-109240 and JP-A-4-324855, put down in writing.The particularly preferred general formula (VIII) and (IX) compound of representative that is to use among the JP-A-4-324855.
The tellurium sensitizer that uses in tellurium sensitizing is can be at the surperficial or inner compound that produces silver telluride of silver halide particle, and the guess silver telluride constitutes sensitizing and examines.Silver telluride in the silver halide emulsus liquid produces speed can be by the method test of putting down in writing in JP-A-5-313284.The object lesson of described compound is included in USP No.1,623,499, the same No.3,320,069, the same No.3,772,031, British patent No.235,211, the same No.1,121,496, the same No.1,295,462, the same No.1,396,696, Canadian Patent No.800,958, JP-A-4-204640, JP-A-4-271341, JP-A-4-333043, JP-A-5-303157, JChem.Soc.Chem.Commun., 635 (1980), the same 1102 (1979), the same 645 (1979), J.Chem Soc.Perkin.Trans., 1,2191 (1980), S.Patai, those that put down in writing among the TheChemistry of Organic Selenium and Tellurium Compounds, Vol.1 (1986) and the same Vol.2 (1987).Wherein, the general formula of JP-A-5-313284 (II), (III) and (IV) compound of representative be preferred.
The selenium sensitizer that the present invention uses or the amount of tellurium sensitizer change with used silver halide particle and chemical slaking condition.Usually, its scope is 10 -8-10 -2The mol/mol silver halide, preferred 10 -7-10 -3Mol.The condition of chemical sensitization of the present invention is not particularly limited, but is 5-8 at pH usually, and pAg is 6-11, preferred 7-10, temperature 40-95 ℃, carries out under preferred 45-85 ℃.
As the noble metal sensitizer, can use gold, platinum, palladium or iridium, wherein golden sensitizing is particularly preferred.The example of the golden sensitizer that uses in the gold sensitizing comprises gold chloride, potassium chloroaurate, golden potassium thiocyanate, aurosulfo, aurothioglucose (I) and sulfo-mannose gold (I).Gold sensitizer consumption about 10 -7-Yue 10 -2The mol/mol silver halide.In the silver halide emulsus liquid that the present invention uses, in silver halide particle formation or physics slaking, can comprise cadmium salt, sulphite, lead salt or thallium salt.
In the present invention, can also use reduction sensitization.As the reduction sensitization agent, can use tin salt, amine, FAS or silane compound.Silver halide emulsus liquid can contain the thiosulfonic acid compound by the method for putting down in writing in European patent (EP) No.293917.Be used for the combination that silver halide emulsus liquid that photosensitive material of the present invention uses can be a kind of emulsion or two or more emulsion (for example, average grain diameter, halogen composition, crystalline state, Chemical Sensitization or photosensitivity different those) in preparation.For obtaining high-contrast,, preferably be coated with the emulsion of ISO in the support vicinity as in JP-A-6-324426, putting down in writing.
＜binding agent 〉
In the emulsus liquid layer, can use binding agent, with even dispersion silver salt particles and help bonding between emulsus liquid layer and the support.As binding agent in the present invention, non-soluble polymer or water-soluble polymer all are suitable for, but water-soluble polymer is preferred.
The example of binding agent comprises gelatin, polyvinyl alcohol (PVA), PVP (PVP), polysaccharide such as starch, cellulose and derivative thereof, poly(ethylene oxide), polysaccharide, polyvinylamine, shitosan, polylysine, polyacrylic acid, poly-alginic acid, poly-hyaluronic acid, carboxycellulose etc.These materials have neutrality, anion or cationic properties according to the ionic nature of functional group.
The amount of the binding agent that contains in the emulsus liquid layer is not particularly limited, and can suitably select in performance dispersiveness and fusible scope.
＜solvent 〉
Be not particularly limited forming the solvent that uses in the above-mentioned emulsus liquid layer.For example, can make water, organic solvent (for example pure as methyl alcohol, ketone such as acetone, acid amides such as formamide, sulfoxide such as dimethyl sulfoxide (DMSO), ester such as ethyl acetate, or ether), ionic liquid or its mixture.
In emulsus liquid layer of the present invention, with respect to the total weight of silver salt contained in the emulsus liquid layer, binding agent etc., the solvent for use amount is 30-90 weight %, preferred 50-80 weight %.
(2) each step
(2-1) exposure
In the present invention, the photosensitive material that is coated with the layer that contains silver salt that is provided with on support is exposed.Can expose with the electromagnetic wave ray.The electromagnetic wave ray can be a light, for example visible light or ultraviolet light, or ray such as X-ray.Can use the light source with Wavelength distribution or the light source of specific wavelength to expose.
As light source, when needed, can use and show photoemissive various luminescent substance in the visible range.For example, emitting red light material, green emitting material or blue-light-emitting material can use separately or use with two or more mixture.Spectral regions are not limited to above-mentioned redness, green and blue region, can also use at yellow, orange, purple or the luminous fluorescent material of infrared region.Especially, often use by mixing the cathode ray tube that these luminescent substances emit white light.Ultra-violet lamp also is preferred, can also use the g-line or the i-line of mercury vapor lamp.
In the present invention, preferably use various laser beams to expose.For example, preferably carry out exposure of the present invention by scanning exposure method, wherein using gases laser, light-emitting diode, semiconductor laser, by the monochromatic high density light that uses semiconductor laser as the second harmonic generator (SHG) that constitutes of the semiconductor laser of exciting light source or solid-state laser and nonlinear optical crystal.In addition, can also use KrF excimer laser, ArF excimer laser or F2 laser.For obtaining compact and cheap system, preferably use semiconductor laser or expose by the second harmonic generator (SHG) that constitutes of semiconductor laser or solid-state laser and nonlinear optical crystal.Especially compact in order to design, cheap, long-life and high stability device, the most preferred semiconductor laser that is to use exposes.
In the situation of using silver halide, exposure energy is preferably 1mJ/cm 2Or lower, more preferably 100 μ J/cm 2Or lower, and more preferably 50 μ J/cm 2Or it is lower.
The object lesson of laser light source comprises the blue semiconductor laser (being delivered at 48th United Meeting of Applied Physics (March calendar year 2001) by Nichia Chemical Co.) of wavelength 430-460nm; The green (light) laser of about 530nm that the semiconductor laser (vibration wave is about 1060nm) of the LiNbO3 SHG crystal by having waveguide type counter-rotating farmland (inverted domain) structure obtains optical wavelength conversion; The red laser diode of the about 685nn of wavelength (Hitachi type: HL6738MG); Red laser diode (Hitachi type: HL6501MG) with the about 650nm of wavelength.
When conveying has the support (being also referred to as film) of the emulsus liquid layer that comprises aforesaid silver salt emulsion, by can contain the pattern exposure of silver salt layer with laser beam (being also referred to as light beam) scan exposure.Especially, preferred capstan winch (capstan) the laser scans exposure device of in JP-A-2000-39677, putting down in writing that uses.Further preferably use the DMD in the optical beam scanning system of in JP-A-2000-1244, putting down in writing, replace the beam flying under the rotation of polygon minute surface in the capstan system.
About using the scan method of light beam, the preferred method of exposing with the vertical orientated linear light sorurce of throughput direction or polygonal rotating mirror of using wherein by using basically.In the case, the light intensity modulation of light beam should be become have two or more values.With continuous dot pattern straight line.Because be continuous point, the fine rule of single-point has stepped edge.The thickness of fine rule is corresponding to the width of narrow part.
As another kind of light scan method, also preferred scanning is fit to inclination and the light beam throughput direction inclination of lattice.In the case, preferably make two scanning light beam quadratures, thereby the luminous intensity of light beam becomes 1 basically on the plane of exposure.
(2-2) development treatment
In the present invention, after the exposure of emulsus liquid layer, carry out development treatment.Can use in emulsion mask that development photographic silver halide film or paper, lithographic printing film, photomask are used etc. technology commonly used to carry out development treatment.Developing solution is not particularly limited, and can use PQ developer, MQ developer or MAA developer.Can also use the commercially available prod, for example, developing solution in developing solution or the kit, CN-16, the CR-56, CP45X, FD-3 or the Papitol that make as Fuji Film Co., perhaps C-41, the E-6, RA-4, D-19 or the D-72 that make of Eastman Kodak Co..Can also make developing solution offscreen.As the lithographic printing developing solution, can use the D85 that for example makes by Eastman Kodak Co..In the present invention,, form the argent part at exposure region by aforesaid exposure and developing process, the argent part of preferred patternization, and in the unexposed area, form light transmission part described later.
As the developing solution in the manufacture method of the present invention, the developer that can use the dihydroxy benzenes class is as developing solution.The example of dihydroxy benzenes developer comprises hydroquinones, chlorohydroquinone, isopropyl hydroquinones, methyl hydroquinone and hydroquinones monosulfonate, and wherein hydroquinones is particularly preferred.Auxiliary developer as to above-mentioned dihydroxy benzenes developer performance excess of export additivity can use 1-phenyl-3-pyrazolone and para-aminophenol.As the developing solution that uses in the manufacture method of the present invention, can preferably use the combination of dihydroxy benzenes developer and 1-phenyl-3-pyrazolone or the combination of dihydroxy benzenes developer and para-aminophenol.
The example of the developer that can make up with the 1-phenyl-3-pyrazolone or derivatives thereof as auxiliary developer comprises 1-phenyl-3-pyrazolone, 1-phenyl-4,4-dimethyl-3-pyrazolone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolone etc.
The example of p-aminophenyl phenols auxiliary developer comprises N-methyl-para-aminophenol, para-aminophenol, N-(beta-hydroxy ethyl)-para-aminophenol, N-(4-hydroxy phenyl) glycine etc., and wherein N-methyl-para-aminophenol is preferred.The usual amounts of dihydroxy benzenes developer is the 0.05-0.8mol/ liter, but preferable amount is 0.23mol/ liter or higher, the more preferably scope that rises at 0.23-0.6mol/ in the present invention.Under the situation of the combination of using dihydroxy benzenes and 1-phenyl-3-pyrazolone or para-aminophenol, preferably the former consumption is the 0.23-0.6mol/ liter, more preferably 0.23-0.5mol/ liter, latter's consumption are that 0.06mol/ rises or littler, more preferably the 0.03-0.003mol/ liter.
In the present invention, preferably develop starting soln and developer make-up solution all has the performance of " make pH increase by 0.5 or littler " under the situation that 0.1mol NaOH is added to 1 liter of solution.By regulating its pH value of development starting soln to be tested or developer make-up solution is 10.5,0.1mol NaOH is added in 1 liter of this solution then, and the pH value of measurement solution, can confirm the development starting soln to be used or this performance of developer make-up solution.When pH increases by 0.5 or more hour, solution is considered to have above-mentioned performance.In manufacture method of the present invention, preferably use in above-mentioned test, to show pH increase by 0.4 or littler development starting soln and developer make-up solution.
For giving development starting soln or the above-mentioned performance of developer make-up solution, the preferred method of utilizing buffer solution of using.As buffer solution, can use carbonate, the boric acid of in JP-A-62-186259, putting down in writing, the carbohydrate of in JP-A-60-93433, putting down in writing (as sucrose), oxime (as acetoxime), phenol (as the 5-sulfosalicylic acid) or tertiary phosphate (as sodium salt or sylvite), preferred carbonate or boric acid.Preferred use amount is a 0.25mol/ liter or higher, the buffer solution (particularly carbonate) that preferred especially 0.25-1.5mol/ rises.
In the present invention, the preferred pH value of development starting soln is 9.0-11.0, preferred especially 9.5-10.7.In addition, when handling continuously, the developer make-up solution in the developing trough and the pH value of developing solution fall into this scope.For regulating pH, can use alkali, it is common water-soluble inorganic alkali metal salt (as NaOH, potassium hydroxide, sodium carbonate or potash).
At the 1m that handles method constructed in accordance 2During photosensitive material, the content of the developer make-up solution in the developing solution is 2000ml or littler, preferred 303-1000ml, preferred especially 50-600ml.The developer make-up solution can have identical composition with the development starting soln.Selectively, about a certain composition that consumes in development, it can have the concentration higher than development starting soln.
The developing solution (following sometimes with " development starting soln " and " developer make-up solution " general designation work " developing solution ") that is used for developing photosensitive material processing of the present invention can contain typical additives (as stabilizer or chelating agent).The example of stabilizer comprises sulphite, as sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium hydrogensulfite, inclined to one side potassium bisulfite, sodium formaldehydebisulfite etc.The preferred amount of sulphite of using is 0.20mol/ liter or higher, and more preferably 0.3mol/ rises or be higher.Yet, preferably be limited to the 1.2mol/ liter on it, because excessively add affiliation and cause that in developing solution silver is dirty.Particularly preferred scope is the 0.35-0.7mol/ liter.Can also use a small amount of ascorbic acid derivates that makes up with sulphite, as dihydroxy benzenes developer stabilizer.The example of ascorbic acid derivates comprises ascorbic acid, as thorn eleostearic acid (erysorbic acid) and its alkali metal salt (as sodium salt or sylvite) of its stereoisomer.As ascorbic acid derivates, from the viewpoint of material cost, the preferred thorn eleostearic acid sodium that uses.The amount of the preferred ascorbic acid derivates that uses and the mol ratio of dihydroxy benzenes developer are 0.03-0.12, preferred especially 0.05-0.10.Using under the situation of ascorbic acid derivates as stabilizer, preferably developing solution does not preferably contain organic boron compound.
Other additive that uses in the developing solution comprises development restrainer, as sodium bromide or KBr; Organic solvent is as ethylene glycol, diethylene glycol, triethylene glycol or dimethyl formamide; Development accelerant, for example, alkanolamine such as diethanol amine or triethanolamine, imidazoles or derivatives thereof; Prevent sulfhydryl compound, indazole compound, benzotriazole cpd or the benzimidazole compound of agent as bloom inhibitor or black pepper spot.The object lesson of above-mentioned benzimidazole compound comprises 5-nitro indazole, 5-p-nitrophenyl formoxyl Aminoindazole, 1-methyl-5-nitro indazole, 6-nitro indazole, 3-methyl-5-nitro indazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenzene and triazolam, 4-[(2-sulfydryl-1; 3; 4-thiadiazoles-2-yl) sulfo-] sodium butane sulfonate, 5-amino-1; 3,4-thiadiazoles-2-mercaptan, methylbenzotrazole, 5-methylbenzotrazole, 2-sulfydryl BTA etc.The common consumption of benzimidazole compound is that 0.01-10mmol/ rises developing solution, more preferably 0.1-2mmol.
Developing solution can also contain the organic or inorganic chelating agent.The example of inorganic chelator comprises sodium tetrapolyphosphate, calgon etc.As organic sequestering agent, can use organic carboxyl acid, aminopolycanboxylic acid, organic phospho acid, aminophosphonic acid or organophosphorus based carboxylic acid basically.
The example of above-mentioned organic carboxyl acid comprises acrylic acid, oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, butanedioic acid, azelaic acid, decanedioic acid, nonane dicarboxylic acids, decane dicarboxylic acid, heneicosane dicarboxylic acid, maleic acid, itaconic acid, malic acid, citric acid, tartaric acid etc., but the invention is not restricted to this.
Above-mentioned aminopolycanboxylic acid's example comprises iminodiacetic acid, NTA, nitrilo-three propionic acid, ethylenediamine monohydroxy ethyl triacetic acid, ethylenediamine tetra-acetic acid, glycol ether tetraacethyl, 1,2-diaminopropanetetraacetic acid, diethylene-triamine pentaacetic acid, triethylenetetraaminehexaacetic acid, 1,3-diaminourea-2-propyl alcohol tetraacethyl, glycoletherdiaminotetraacetic acid and the compound of in JP-A-52-25632, JP-A-55-67747, JP-A-57-102624 and JP-B No.53-40900, putting down in writing.
The example of organic phospho acid is included in USP No.3, and 214,454, USP No.3,794,591 and GP-A No.2227639 in the hydroxy alkylidene di 2 ethylhexyl phosphonic acid put down in writing, perhaps at ResearchDisclosure, vol.181, the compound of record in 18170 (in the May, 1979).
The example of aforesaid aminophosphonic acid comprises amino three (methylene phosphonic acids), ethylenediamine tetramethylene phosphonic acid ATMP or the like.In addition, can also use disclosed compound among No. 18170, JP-A-57-208554, JP-A-54-61125, JP-A-55-29883 and the JP-A-56-97347 at ResearchDisclosure.
Phosphinocarboxylic acid's example is included in the compound of putting down in writing among JP-A-52-102726, JP-A-53-42730, JP-A-54-121127, JP-A-55-4024, JP-A-55-4025, JP-A-55-126241, JP-A-55-65955, JP-A-55-65956 and the Research Disclosure No.18170.Chelating agent can use with the form of alkali metal salts or ammonium salt.
By per 1 liter of developing solution, the preferred addition of chelating agent is 1 * 10 -4-1 * 10 -1Mol, more preferably 1 * 10 -3-1 * 10 -2Mol.
Developing solution can also contain the compound of putting down in writing and prevent agent as silver-colored dirt in JP-A-56-24347, JP-A-56-46585, JP-B-62-2849 and JP-A-4-362942.As secondary solvent, can also use the compound of in JP-A-61-267759, putting down in writing.Developing solution can also contain toner, surfactant, defoamer, curing agent etc. where necessary.Development temperature and developing time are interrelated, and according to determining total processing time.Yet development temperature is preferably about 50 ℃ of about 20-, more preferably 25-45 ℃ usually.Developing time was preferably 5 seconds-2 minutes, more preferably 7-90 second.
For saving the space of cost of transportation, packing cost and developing solution, also embodiment preferred is to concentrate developing solution and dilution before using.For concentrating developing solution, be to use sylvite effectively as salt contained in developing solution.
Thereby the development treatment among the present invention can comprise the photographic fixing that is used for removing the silver salt realization stabilisation of unexposed area and carries out and handle.For example can use photographic silver halide film or paper, lithographic printing film or photomask with the emulsion mask in the photographic fixing carried out among the present invention of photographic fixing technology commonly used handle.
The preferred component of the photographic fixing solution that uses in the photographic fixing step is as follows.
Promptly, preferably photographic fixing solution contains sodium thiosulfate or ATS (Ammonium thiosulphate), and contains tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tiron, ethylenediamine tetra-acetic acid, diethylenetriamine pentaacetic acid, nitrotrimethylolmethane acetate, its salt etc. when needed.Viewpoint from the environment in recent years protection does not preferably contain boric acid.The example of the fixer in the photographic fixing solution that uses among the present invention comprises sodium thiosulfate, ATS (Ammonium thiosulphate) etc.From the viewpoint of fixation rate, ATS (Ammonium thiosulphate) is preferred.Yet,, can also use sodium thiosulfate from the viewpoint of environment in recent years protection.Although the amount of this known fixer can suitably change, its common scope is the about 2mol/ liter of about 0.1-, preferred 0.2-1.5mol/ liter.When needed, photographic fixing solution can contain curing agent (as water soluble aluminum compound), stabilizer (as sulphite or bisulfites), pH buffer solution (as acetate), pH conditioning agent (as ammonia or sulfuric acid), chelating agent, surfactant, humidizer, photographic fixing promoter etc.
The example of above-mentioned surfactant comprises anion surfactant, as sulphate cpd or Sulfonated compound, and polyvinyl surfactant, or the amphoteric surfactant of in JP-A-57-6740, putting down in writing.In addition, photographic fixing solution can contain known defoamer.
The example of above-mentioned humidizer comprises alkanolamine, alkane glycol etc.As photographic fixing promoter, can also use the thiourea derivative of in JP-B-5-35754, JP-B-58-122535 and JP-B-58-122536, putting down in writing; The alcohol that in molecule, has triple bond; At USP No.4, the sulfide compound of record in 126,459; The mesoionic of in JP-A-4-229860, putting down in writing (mesoion) compound; Or the compound of in JP-A-2-44355, putting down in writing.The example of above-mentioned pH buffer solution comprises organic acid, as acetate, malic acid, butanedioic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic or adipic acid; With inorganic buffer solution, as boric acid, phosphate or sulphite.The pH buffer solution is preferably acetate, tartaric acid or sulphite.The pH buffer solution is used for preventing to be carried developing solution and increases at photographic fixing solution pH, and preferably its amount is 0.01-1.0mol/ liter, more preferably 0.02-0.6mol/ liter.Preferred its pH value of photographic fixing solution is 4.0-6.5, preferred especially 4.5-6.0.As the dyestuff dissolution accelerator, can also use the compound of in JP-A-64-4739, putting down in writing.
The example of the curing agent that uses in the photographic fixing solution of the present invention comprises water-soluble aluminum salt and chromic salts.Preferably curing agent is a water-soluble aluminum salt, and as aluminium chloride, aluminum sulfate or alum, preferred addition is the 0.01-0.2mol/ liter, more preferably the 0.03-0.08mol/ liter.
In above-mentioned photographic fixing step, fixing temperature is preferably about 20 ℃-Yue 50 ℃, and more preferably 25-45 ℃, fixing time was preferably 5 seconds-1 minute, more preferably 7-50 second.With respect to the treating capacity of photosensitive material, the magnitude of recruitment of photographic fixing solution is preferably 600ml/m 2Or littler, more preferably 500ml/m 2Or littler, preferred especially 300ml/m 2Or it is littler.
The photosensitive material that had carried out development and photographic fixing processing preferably carries out water rinse to be handled or stabilization processes.In water rinse processing or stabilization processes, for every m 2Photosensitive material, carry out rinsing through commonly used 20 liters or water still less, magnitude of recruitment is 3 liters or still less (comprises 0, i.e. rinsing in vertical water-bath).Therefore, not only can save water, and save the pipeline in automatic processor.Be to reduce the magnitude of recruitment of washings, known have multistep (2-or 3-step) contracurrent system.In manufacture method of the present invention, use under the situation of above-mentioned multistep contracurrent system,,, thereby can carry out more effective rinsing promptly towards by the littler Treatment Solution of photographic fixing contaminated aqueous solution with the photosensitive material after the proper orientation processed in sequence photographic fixing step.In addition, carrying out with low amounts of water under the situation of rinsing, preferably providing to have compression roller of in JP-A-63-18350 and JP-A-62-287252, putting down in writing or the potcher that intersects roller.In addition, in order to alleviate the pollution that causes with the low amounts of water rinsing, can use the combination that adds various oxidants or filter with filter.In addition, in described method, overflow liquid or the described overflow liquid of part from rinsing bath or stabilisation bath, it replenishes rinsing bath or stabilisation by water and bathes and produce, and comprises in the pretreatment steps that the mildew-resistant device can put down in writing in JP-A-60-235133 and be used as the Treatment Solution with photographic fixing ability.In addition, can add water soluble surfactant active or defoamer, produce the bubble pattern and/or will handle composition is transferred to processing from compression roller film preventing the time with the low amounts of water rinsing.
In addition, in water rinse processing or stabilization processes, the dye absorbent of putting down in writing in JP-A-63-163456 can place rinsing to bathe, thereby prevents from the pollution of the dyestuff of photosensitive material stripping.In addition, in the stabilization processes after rinsing is handled, the bath that contains the compound of putting down in writing in JP-A-2-201357, JP-A-2-132435, JP-A-1-102553 and JP-A-46-44446 can be as the final bath of photosensitive material.In this case, when needed, can add metallic compound, fluorescent whitening agent, chelating agent, film pH conditioning agent, curing agent, bactericide, mould inhibitor, alkanolamine or the surfactant of ammonium compounds, for example Bi or Al etc.The water that uses in rinsing processing or the stabilization processes can be running water, or preferred deionized water or with the water after halogen, ultraviolet germicidal lamp or oxidant (as ozone, hydrogen peroxide or the perchlorate) sterilization.Can also use the washings that contain the compound of in JP-A-4-39652 and JP-A-5-241309, putting down in writing.Water rinse handle or stabilization processes in, preferably use bath temperature 0-50 ℃ and bathe in 5 seconds-2 minutes time.
Treatment Solution of using among the present invention such as developing solution or photographic fixing solution are preferably kept in the packaging material of the low oxygen permeation degree of putting down in writing among the JP-A-61-73147.For reducing magnitude of recruitment, further preferably the contact area of treatment trough and air is less, to avoid solution evaporation and atmospheric oxidn.Roller transmission type automatic processor for example is documented in USP No.3, in 025,779 and 3,545,971, is called for short below and makes the roller transport processor.The roller transport processor preferably includes development, photographic fixing, rinsing and dry four steps.Although these four steps are most preferably used in the present invention, do not get rid of other step (as stopping step).In addition, can use stabilization step to replace rinse step in these four steps.
In each above-mentioned steps, the composition of developing solution or photographic fixing solution can anhydrate with the solid supply by removing, and can be dissolved in before use in the water of scheduled volume and form developing solution or photographic fixing solution.The processing material of this form is known as the solids treatment material.The solids treatment material uses with the form of powder, tablet, particle, block or pastel.The preferred form of handling material is form or the tablet of putting down in writing in JP-A-61-259921.Described tablet can be by for example at JP-A-51-61837, JP-A-54-155038, JP-A-52-88025 and BP No.1, the common method manufacturing of record in 213,808.The solids treatment material of particle form can be by the common method manufacturing of for example putting down in writing in JP-A-2-109042, JP-A-2-109043, JP-A-3-39735 and JP-A-3-39739.The processing material of powder type can be by for example at JP-A-54-133332, BP No.725, the common method manufacturing of record in 892 and 729,862 and GP No.3,733,861.
Consider solubility, preferred its bulk density of solids treatment material is 0.5-6.0g/cm 3, more preferably 1.0-5.0g/cm 3
Be preparation solids treatment material, can use following method: be included in the material that constitutes the processing material, provide reactive materials with layered mode, make at least two kinds of reacting to each other property particulate matters constitute the layer that the intermediate section interlayer of the material of reactive materials inertia is separated by one deck at least, use then can vacuum-packed bag as packaging material, find time and seal this bag.In this specification, can not react under the common state of material in packing that the term 'inertia' refers to be in contact with one another, noticeable response can not take place yet.Active material can be not inertia to two kinds of reacting to each other property materials, can be inertia in the expection of two kinds of reacting to each other property materials is used perhaps.In addition, inert substance is the material that uses simultaneously with two kinds of reactive materials.For example, in developing solution, because hydroquinones directly contacts with NaOH, so sodium sulfite etc. can be as the separate layer between hydroquinones in the vacuum packaging and the NaOH, thereby can preserve for a long time.In addition, hydroquinones etc. can be made into spherical, thereby reduce the contact area with NaOH, thereby improve retention and can use with mixture.As vacuum-packed packaging material, the bag that can use the laminated thing by inert plastic film or plastic material and metal forming to form.
By the weight of silver contained in the exposure region before the exposure, the weight of contained argent is preferably 50 weight % or bigger in the development treatment post-exposure district, more preferably 80 weight % or bigger.Preferably by the weight of silver contained in the exposure region before the exposure, its amount of argent contained in the exposure region is 50 weight % or bigger, because can obtain high conductivity in this case.
Although be not particularly limited, preferably be higher than 4.0 for the grade of carrying out after the development treatment of the present invention.Grade after the development treatment is higher than 4.0 can increase conducting metal conductivity partly, keeps the high grade of transparency of light transmission part simultaneously.Being higher than 4.0 grade can be by for example realizing by above-mentioned the doping with rhodium ion or iridium ion.
(2-3) physical development and electroplating processes
In order giving by exposure and the argent of development treatment, preferably to carry out physical development and/or electroplating processes in the present invention, thereby make argent partly have conducting metal particles partly with conductivity.In the present invention, conducting metal particles can be carried on the argent part by one of physical development and electroplating processes.In addition, argent is partly gone up load has conducting metal particles to realize by combination physical development and electroplating processes.The argent part of having carried out physical development and/or electroplating processes is known as " conducting metal part " sometimes.
The term that uses among the present invention " physical development " refers to come reducing metal ion such as silver ion with reducing agent, with plated metal particle on the nuclear of metal or metallic compound.This physical development is with the B﹠amp that shows in sight; The M film, promptly show in synovial membrane or the preparation printed panel, these technology are also in the present invention available.
Physical development can be carried out simultaneously with the development treatment after the exposure, or carries out separately after development treatment.
In the present invention, electroplating processes can be electroless plating (electronation plating or displacement plating) or metallide.Selectively, can use electroless plating and metallide simultaneously.
Next, the preferred embodiment that metallide is handled will be described in detail with reference to the attached drawings.Be fit to carry out the electroplating device that above-mentioned metallide handles and have following structure: wherein from living through the exposure of emulsus liquid layer around the unwinding shaft (not shown) that film is arranged and the film of developing process infeeds the metallide groove continuously, and after plating is finished, twine film continuously around twining the axle (not shown).
Fig. 1 has shown the metallide groove that is suitable in the aforesaid metallide processing.By metallide groove (10) as shown in fig. 1, can continuous electroplating long film (16) film of development treatment (stood as mentioned above to expose and).Arrow is represented the throughput direction of film (16).Metallide groove (10) provides the plating bath (11) that has wherein compiled plating bath (15).In plating bath (11), the parallel a pair of positive plate (13) that provides.At a pair of deflector roll of positive plate (13) intermediate arrangement (14), make its can with the parallel rotation of positive plate (13).Deflector roll (14) can vertical moving, thereby can regulate the electroplating processes time of film (16).
In plating bath (11) top, with rotatable mode separately provide a pair of feed roller (negative electrode) (12a, 12b).In plating bath (11) top, rotatably provide draining roller (17) in outlet side feed roller (12b) below.Between this draining roller (17) and feed roller (12b), provide washing sprayer unit (not shown) from film, to remove plating bath.
By the electric wire (not shown) positive plate (13) is connected with the positive terminals of power supply (not shown), and feed roller (12a 12b) is connected with the negative terminals of power supply (not shown).
Have in the situation of the size of 10 * 10 * 10cm to 100 * 200 * 300cm for example at metallide groove (10), preferably (distance L shown in Fig. 1 a) is adjusted into 0.5-15cm, more preferably 1-10cm and more preferably 1-7cm with the bottom part of the contact-making surface of entrance side feed roller (12a) and film (16) and the distance between the plating bath face.Also preferably the bottom part of the contact-making surface of outlet side feed roller (12b) and film (16) and the distance (the distance L b shown in Fig. 1) between the plating bath face are adjusted into 0.5-15cm.
Next, will illustrate that the electroplating device that possesses aforesaid metallide groove (10) by use forms the method for copper coin on the net-like pattern of film.
At first, in plating bath (11), compile plating bath (15).As plating bath, can use the solution that comprises 30-300g/L Salzburg vitriol and 30-300g/L sulfuric acid.In the situation of nickel plating, can use the solution that comprises nickelous sulfate, nickel chloride etc.In silver-plated situation, can use the solution that comprises silver cyanide etc.Plating bath also further comprises additive for example surfactant, sulphur compound or nitrogen compound.
Film (16) is in the state that twines around the unwinding shaft (not shown).Then, twine film (16), make that (12a 12b) contacts for side that coating is formed by film (16) and feed roller around the conveying roller (not shown).At once, the sheet resistance of film is preferably 1-1000 Ω/ before metallide, more preferably 5-500 Ω/, and more preferably 10-100 Ω/.
On the sunny side pole plate (13) and feed roller (12a, 12b) apply voltage and with feed roller (12a, 12b) contact time transport membrane (16).Film (16) is sent in the plating bath (11), and wherein film is immersed in the plating bath (15) to form copper coating.When film passes draining roller (17), wipe the plating bath that adheres to film (16) and be recovered in the plating bath (11).In a plurality of metallide grooves, repeat this process.After in the end washing with water, twine film around twining the axle (not shown).
Preferably the transporting velocity with film (16) is made as 1-30m/min.More preferably the transporting velocity of film (16) is 1-10 to 30m/min, more preferably 2-5m/min.
Although the quantity of metallide groove is not particularly limited, preferred 2-10 groove, more preferably 3-6 groove of using.
Apply voltage preferably at 1-100V, more preferably in the scope of 2-60V.In the situation that two or more metallide grooves are provided, the preferred voltage that is applied on the metallide groove that progressively reduces.The magnitude of current in also preferred first groove inboard is 1-30A, more preferably 2-10A.
Also (12a 12b) contacts (based on total contact area, the area ratio of electricity contact reaches 80% or bigger basically) to the preferred feedstock roller with whole film surface.
Before in aforesaid metallide is bathed, carrying out electroplating processes, preferably wash and pickling.As the Treatment Solution of in pickling, using, can use the solution that comprises sulfuric acid etc.
Electromagnetic shielding material is used for display situation under, the coat of metal of Xing Chenging preferably has as far as possible little thickness thus, to increase display viewing angles.As under the situation of conductive wires material,, need film thinner for obtaining more high density.From these viewpoints, the layer that the conducting metal of electroplating thus forms preferably has thickness less than 9 μ m, more preferably 0.1 μ m or bigger but less than 5 μ m, more preferably 0.1 μ m or bigger but less than 3 μ m again.
In electroplating process of the present invention, can also before metallide, carry out electroless process.
In carrying out electroless situation, can use known electroless plating techniques, for example be used for the electroless plating techniques of printed substrate, preferably electroless copper.
The example of the chemical substance that comprises in the plating solution for electroless copper plating comprises copper sulphate or copper chloride, reducing agent is formalin or glyoxalic acid for example, the copper part is EDTA or triethanolamine for example, and is used to bathe stable and the additive that improves the electroplated film disk smoothness for example polyethylene glycol, ferrocyanic acid salt or bipyridine.
The conductive pattern on the film even be continuous (not being that electricity is interrupted) at its part place further preferably.When conductive pattern is interrupted, the danger that the some parts that the metallide that exists in plating is not electroplated in bathing becomes uneven.
Can carry out electroplating processes under the electroplating velocity condition of gentleness or under 5 μ m/hr or higher high electroplating velocity.In electroplating processes, can use various additives, as part, EDTA for example is to improve the stability of electroplating solution.
(2-4) oxidation processes
In the present invention preferably, the argent after development treatment part and the conducting metal portion that forms by physical development and/or electroplating processes are carried out oxidation processes.By carrying out oxidation processes, can remove the metal that finally is deposited on slightly in the light transmission part, thereby in the light transmission part, obtain about 100% transparency.
Can carry out oxidation processes by the known treatment of utilizing various oxidants, as using Fe (III) ion processing.As mentioned above, can or after physical development or electroplating processes, carry out oxidation processes after exposure and development treatment emulsus liquid layer.Can also carry out oxidation processes after development treatment and after physical development or the electroplating processes.
In the present invention, can also be with the solution-treated argent part that contains Pd after exposure and development treatment.Pd can be divalence palladium ion or metal Pd.Because this processing can be quickened electroless plating or physical development.
(3) conducting metal part
Be used as under the situation of light-transmitting electromagnetic shielding material, conducting metal part of the present invention preferably has by triangle such as equilateral triangle, isosceles triangle or right-angled triangle, quadrangle is as square, rectangle, rhombus, parallelogram or trapezoidal, just (n)-polygon such as regular hexagon or octagon, circle, the geometry that is combined to form of ellipse or star, more preferably by these geometries constitute netted.From the viewpoint of EMI shielding properties, triangle is the most effective, but considers visible light transmissivity, and just (n)-polygon that the n value is bigger is favourable, because provide bigger aperture opening ratio for identical live width, thereby has improved visible light transmissivity.For minimizing ripple, further preferably provide with at random or the aperiodicity mode change the geometry of live width.
Be used as under the situation of conductive wires material, the shape of conducting metal part is not particularly limited, and can select shape arbitrarily according to purposes.
As under the situation of light-transmitting electromagnetic shielding material, the fine rule in the conducting metal part should be adjusted to 1 μ m or bigger but be no more than 40 μ m, preferred 5 μ m or bigger but be no more than 30 μ m, most preferably 10 μ m or bigger but be no more than 25 μ m.Line is preferably 50 μ m or bigger but be no more than 500 μ m at interval, more preferably 200 μ m or bigger but be no more than 400 μ m, most preferably 250 μ m or bigger but be no more than 350 μ m.Be purposes such as ground connection, the conducting metal part can have the part that live width surpasses 20 μ m.
When considering visible light transmissivity, preferred its aperture opening ratio of conducting metal part of the present invention is 85% or higher, more preferably 90% or higher, most preferably 95% or higher.In this specification, term " aperture opening ratio " refers to constitute netted fine rule exterior section shared ratio in whole area, and for example, its aperture opening ratio of square lattice net of live width 15 μ m and spacing 300 μ m is 90%.
(4) light transmission part
Term " light transmission part " refers to the part with transparency the conducting metal part in the light-transmitting electromagnetic screened film as used herein.As mentioned above, " transmitance of light transmission part " refers to have the part of the transmitance of being represented by minimum transmitance in the 380-780nm wavelength zone, do not comprise the absorption of support and the contribution of reflection, its transmitance is 90% or higher, more preferably 95% or higher, preferred again 97% or higher, more more preferably 98% or higher.Most preferably 99% or higher.
The preferably continuous 3m or longer of the net-like pattern of the conducting metal part among the present invention.Pattern with big repeat number is preferred, because can reduce the loss in making the filter material like this.On the other hand, repeat number increases and to cause following problem through regular meeting: for example when batching rolling, roller diameter increases, and it is heavy that roller becomes, and the pressure at roller center raises, and causes to comprise bonding and trouble such as distortion.Therefore, preferably the length of net-like pattern is no longer than 2000m, preferred 100m or longer but no longer than 1000m, more preferably 200m or longer but no longer than 800m, most preferably 300m or longer but no longer than 500m.
By the same token, the thickness of support is preferably 200 μ m or littler, more preferably 20 μ m or bigger but be no more than 180 μ m, most preferably 50 μ m or bigger but be no more than 120 μ m.
Statement as used herein " intersects the pattern that constitutes mutually by substantially parallel straight fine rule " and refers to so-called grid pattern, and the contiguous fine rule that wherein constitutes grid pattern is parallel, or is arranged in parallel in ± 2 ° of angles.
Preferably, make net-like pattern among the present invention with respect to 30 °-60 ° at throughput direction angle of inclination, more preferably 40 °-50 °, most preferably 43 °-47 °.This is because have with respect to the tilt mask of about 45 ° net-like pattern of framework and be difficult to usually make, and is attended by some problems, comprises inhomogeneities occurring and cost raises.On the other hand, in said method, inhomogeneities is smaller in the time of about 45 °, therefore, compares with the photolithography of mask alignment exposure system or by screen printed patternization, and the present invention has remarkable advantage.
[functional layer of light-transmitting electromagnetic screened film]
(1) infrared ray shielding layer
Light-transmitting electromagnetic screened film according to the present invention has infrared shield character (particularly near-infrared shielding character).As mentioned above, because plasma scope produces strong near infrared ray, so filter not only should block electromagnetic wave, and answers the block near infrared line, thus make practical no problem.Therefore, the transmitance of wavelength zone 800-1000nm must be adjusted to 25% or littler, preferred 15% or littler, more preferably 10% or littler.
As concrete execution mode, can exemplify: (1) comprises the infrared ray absorbing dyestuff in support; (2) comprise the infrared ray absorbing dyestuff in the layer on being formed at support.
Because can improve the durability of infrared ray absorbing dyestuff, execution mode (1) is preferred and thereby can reduces the number of steps for preparing the light-transmitting electromagnetic screened film.In execution mode (1), maybe can absorb ultrared metal complex and can prepare the light-transmitting electromagnetic screened film by in aforesaid support, adding the infrared ray absorbing dyestuff that will be described below.More particularly, can exemplify (I) and comprise that kneading is used for the resin and the infrared ray absorbing dyestuff of support, form the method for support then by hot-moulded; (II) be included in polymerization catalyst and have the method that forms support down with the performed polymer cast polymerization infrared ray absorbing dyestuff of resin monomer or resin monomer.
In execution mode (2), can prepare the light-transmitting electromagnetic screened film by coating coating composition on support, described composition comprises the infrared ray absorbing dyestuff that will be described below maybe can absorb ultrared metal complex, solvent, transparent resin etc.In the case, can with the application step of aforesaid emulsus liquid layer simultaneously or be coated with afterwards.By with the application step of aforesaid emulsus liquid layer simultaneously or be coated with afterwards, can form the light-transmitting electromagnetic screened film efficiently, thereby boost productivity.Can also form layer (being called infrared ray shielding layer, infrared ray blocking layer or infrared ray absorbing layer) by sputtering method with infrared shield character.
The coating process that forms infrared ray shielding layer can be selected from dip-coating method, method of roll coating, spraying method, intaglio plate coating process, mould coating process etc.Described coating process can be used for continuous processing, and therefore productivity ratio is better than the batch-type deposition process.Alternatively, can use spin coating method, can form thin and film uniformly by this method.
In execution mode (2), with metallic silver portion branch same side or its opposite side in pass support can form comprise the infrared ray absorbing dyestuff the layer (infrared ray blocking layer).Also preferably add infrared ray absorbing dyestuff etc., thereby give adhesive layer infrared shield character to the composition that is used for adhesive layer that will be described below.
In addition, can form two-layer or more multi-layered infrared ray blocking layer.In the case, can form two-layer or more multi-layered infrared ray blocking layer according to the method for describing in [0039]-[0049] section in JP-A-2001-14206.
In order to obtain effective near-infrared shielding effect, the thickness of preferred infrared ray shielding layer is 0.5 μ m or bigger.From removing residual solvent easily and be carried out to the angle of membrane process easily the film forming step, preferred described thickness is 20 μ m or littler.Preferred especially described thickness is in the scope of 1-10 μ m.
(infrared ray absorbing dyestuff)
As the infrared ray absorbing dyestuff, can use diimmonium (diimonium) compound.The example of Diimmonium compound comprises the compound by the general formula of describing (2) representative in JP-B-43-25335.As the instantiation of the compound of representing by described general formula (2), can quote N, N, N ', N '-four (to the lignocaine phenyl)-1,4-benzoquinone-Diimmonium salt etc.Can randomly synthesize and use this compound.Alternatively, can use commercially available compound.Diimmonium compound has the strong absorbance of molar absorption coefficient about 100,000 in the near infrared region of 900-1100nm wavelength.Although have the fallow color that sees through to green because it shows some absorption in the visible region of 400-500nm wavelength, it is better than other near-infrared absorbing dyestuff aspect visible light transmittance rate.
As Diimmonium compound, can use compound by the disclosed general formula of JP-A-2003-75628 (3) representative.
Although the content of Diimmonium compound depends on the thickness of infrared ray shielding layer, in order to realize practical infrared shield character, (wavelength: 900-1000nm) light transmittance should be adjusted to 20% or littler to its near infrared ray.At the thickness that infrared ray shielding layer is set is in the situation of about 1 to about 20 μ m thickness, therefore the separation (segregation) of compound and the angle of visible transparency from infrared ray shielding layer, the total amount of preferably controlling compound is that per 100 weight portion transparent resins about 0.05 are to about 5.0 weight portions.
In order to give infrared ray shielding layer actual available durability, preferred use has 190 ℃ or more dystectic Diimmonium compound as mentioned above.Fusing point is lower than 190 ℃ compound and is easy to sex change under high temperature and high humility.By using having 190 ℃ or more dystectic compound and selecting suitable resin kind of to discuss hereinafter, can set up actual available durability.
For control near infrared ray (wavelength: thus 900-1000nm) light transmittance is 20% or followingly realizes actual available near infrared ray absorbing matter, preferred one or more near-infrared absorbing dyestuffs that use are as the second kind of near-infrared absorbing dyestuff that is added in the near-infrared absorbing resin combination, its separately maximum absorption wavelength be 750-900nm and do not absorb basically, for example absorption coefficient and 450nm (blue centre wavelength) under the maximum absorption wavelength at visible region, 550nm (green centre wavelength) and 620nm (red centre wavelength) down absorption coefficient ratio each naturally 8.0 or more than.
The absorption coefficient ratio be 8.0 or littler arbitrary situation be not preferred.This is because in this case, arbitrary visible light transmittance rate under 450nm (blue centre wavelength), 550nm (green centre wavelength) and 620nm (red centre wavelength) becomes 65% or littler, the near infrared ray light transmittance that is equivalent under the 800-900nm of actual needs is 20% or littler, and the reduction of this visible light transmittance rate causes seeing through the optical colour of near infrared ray absorption layer.On the other hand, preferably each self absorption factor ratio is 8.0 or bigger, thereby the problems referred to above can not take place.In addition, in the case, can set up 68% or bigger visible light transmittance rate, as the near-infrared shielding compound that also has the antireflection rete that will be described below, this is suitable.
As under 750-900nm, having absorption maximum and respectively doing for oneself 8.0 or the example of above near-infrared absorbing dyestuff, can exemplify two mercaptan nickel complexes, indoline (indolium) compound, phthalocyanine compound and naphthalene phthalocyanine (naphthalocyanine) compound in the absorption coefficient under the maximum absorption wavelength and the ratio of absorption coefficient under 450nm (blue centre wavelength), 550nm (green centre wavelength) and 620nm (red centre wavelength).Wherein, because generally have excellent durability, can suitably use phthalocyanine compound and naphthalene phthalocyanine compound.But, because the latter is more expensive and preferably use the former.
In recent years, advised the many kinds of phthalocyanine compounds that have absorption maximum in the near infrared region, they are by introducing conjugated pi electron system substituting group such as phenyl or obtaining to wherein introducing a large amount of electron substituent group such as alkoxyls given in phthalocyanine frame.Wherein, can suitably use phthalocyanine compound by the general formula of in JP-A-2002-138203, describing (3) representative because its aforesaid absorption coefficient ratio respectively do for oneself 8.0 or more than.
Can also use anthraquinone compounds.As anthraquinone compounds, can use compound by the general formula of in JP-A-2003-75628, describing (1) or (2) representative.
In addition, can use phthalocyanine compound or naphthalene phthalocyanine as the infrared ray absorbing dyestuff.Wherein, the preferred use by the phthalocyanine compound of the general formula of in JP-A-2003-222721, describing (1) representative or by naphthalene phthalocyanine in same document formula of (2) representative.
Except aforesaid dyestuff, can exemplify polymethine compound, metal complex, ammonium compounds, imonium (imonium) compound, Diimmonium compound, anthraquinone compounds, dithiol metal complex compound, naphthoquinone compound, indoxyl compound, azo-compound, triallyl methane compounds and water-soluble dye for example indolenine cyanines and oxole barbiturates salt dyestuff, but the invention is not restricted to this.Being used for electronic installation heat absorption ray or preventing in the situation of noise, preferably use the near-infrared absorbing dyestuff of maximum absorption wavelength as 750-1100nm.Therefore, preferably use metal complex dyes, ammonium dyestuff, phthalocyanine dye, naphthalene phthalocyanine dye or diimmonium dyestuff.
Can be not dissolved in form coating water-soluble dye for example indolenine cyanines and oxole barbiturates salt dyestuff in the organic solvent with the aqueous solution, from reduce environmental impact and reduce the coating cost angle this be favourable.
In order to set up the infrared shield effect effectively, preferably using based on the transparent resin consumption is 0.1 weight % or more, more preferably 2 weight % or more infrared ray absorbing dyestuff.In order to keep the physical property of transparent resin, the also preferred content of adjusting the infrared ray absorbing dyestuff is no more than 10 weight %.
(metal complex)
As metal complex, can use metal complex by general formula (1) or general formula (2) representative as in JP-A-2003-262719, describing.
Although the concentration of metal complex changes according to the thickness of infrared ray blocking layer, required absorption intensity, required visible light transmittance rate etc., the weight based on transparent resin is the scope of 0.1-30% usually.
(other dyestuff)
Can also add one or more maximum absorption wavelengths and drop on interior color correction (color correction) dyestuff of 300-800nm scope.As the example of color correction dyestuff, can exemplify dyestuff commonly used for example inorganic pigment, organic pigment and organic dyestuff.
As organic dyestuff, can use the soluble ketone of wherein resin or ester or soluble lipid-soluble dye or the organic solvent soluble dyestuff in aromatic solvent that will be described below.As organic pigment, can use AZOpigments, phthalocyanine color, quinacridone pigment, dioxadiene (dioxadine) pigment or the like.
The example of inorganic pigment comprises cobalt dyestuff, iron dyestuff, chrome dye, titanium dyestuff, vanadium dyestuff, zirconium dyestuff, molybdenum dyestuff, ruthenium dye, platinum dyestuff, ITO dyestuff, ATO dyestuff or the like.The example of organic pigment and organic dyestuff comprises the aluminium dyestuff, cyanine dyes, the mellocyanine dyestuff, croconium pigment, the squarium dyestuff, the azlenium dyestuff, polymethin dye, naphthoquinone dyestuff, pyrylium dye, phthalocyanine dye, the naphthalene phthalocyanine dye, naphthalene lactams dyestuff, azo dyes, condense azo dyes, indigo dye, perinone dyestuff perylene dyestuff dioxadiene dyestuff, the quinacridone dyestuff, the isoindoline ketone dyes, Kui naphthalene ketone dyes, pyrroles's dyestuff, the thioindigo dyestuff, metal complex dyes, dithiol metal coordination thing dyestuff, the indoxyl dyestuff, triallyl methane dye etc.In these dyestuffs, metal complex dyes, ammonium dyestuff, phthalocyanine dye, naphthalene phthalocyanine dye, pyrroles's dyestuff etc. are preferred.
Be the scope of 0.1-10.0 weight % based on the solid matter overall control of transparent resin and all dyestuffs preferably with the amount of color correction dyestuff.By using 0.1 weight % or more color correction dyestuff, can set up the ability of enough correction colors.Be no more than 10 weight % by adjusting its consumption, can control the interaction between dyestuff and can realize favourable dye stability.Put from these, especially preferably controlling its consumption is 1.0-9.0 weight %.
(transparent resin)
The composition that is preferred for infrared ray blocking layer comprises and is used to form the transparent resin of filming.The instantiation of transparent resin comprises polyethylene, polystyrene, polyacrylic acid, polyacrylate, vinyl compound such as polyvinyl acetate, polyacrylonitrile, polyvinyl chloride and polyvinyl fluoride, the addition polymers of these vinyl compounds, polymethylacrylic acid, polymethacrylates, Vingon, polyvinylidene fluoride, polyvinylidene cyanide, the copolymer of vinyl compound or fluorine compounds is vinylidene fluoride/trifluoro-ethylene copolymer for example, the for example poly-trifluoro-ethylene of vinylidene fluoride/tetrafluoroethylene copolymer and vinylidene dinitrile/vinyl acetate copolymer, fluoride resin, polytetrafluoroethylene and polyhexafluoropropylene, polyamide is nylon 6 and nylon 66 for example, polyimides, polyurethane, polypeptide, polyester is PETG for example, polyethers is Merlon for example, polyoxymethylene, poly(ethylene oxide) and PPOX, epoxy resin, polyvinyl alcohol, polyvinyl butyral resin etc.Yet the present invention is not restricted to this and preferred uses that have can be as the resin of the high rigidity of glass replacement and the high grade of transparency, thermosetting resin thioxanthamide resin, optical resin ARTON for example for example TM(making), ZEONEX by JSR company TM(making), OPTOREZ by ZEON company TM(by HITACHICHEMICALCo., Ltd. makes) or O-PET TM(making) by KANEBO.
In aforesaid resin, the preferably clear resin is that glass transition temperature is 70 ℃ or higher acrylic resin or methacrylic resin.When the glass transition temperature of transparent resin was lower than 70 ℃, resin was softening in 70 ℃ or higher high temperature following time in long term exposure, the easy sex change of Diimmonium compound in the near-infrared shielding simultaneously.As a result, influence their long-time stability, promptly colour balance damages or the near-infrared shielding properties deterioration inadvisablely.On the other hand, when its glass transition temperature is 70 ℃ or when higher, can prevent to comprise the thermal denaturation of the near-infrared absorbing dyestuff of dyestuff, particularly Diimmonium compound.As the resin that satisfies these demands, can exemplify polyester-based resin, acrylic resin, methacrylic resin etc.Consider the dyeing property of basic-dyeable fibre Diimmonium compound, can suitably use acrylic resin or methacrylic resin.
In the presence of polymerization catalyst in the situation of the performed polymer of polymer resin monomer or resin monomer, can be during this process molded many resins.For example, can use resin monomer, as acrylic resin, diethylene glycol (DEG) two (allyl carbonate) resin, epoxy resin, phenolic resins, polystyrene resin, polysulfide or organic siliconresin.Wherein, because can obtain the acryloyl substrate of excellence aspect hardness, thermal endurance and chemical resistance, so the block polymerization of methyl methacrylate is preferred.As polymerization catalyst, can use the free radical thermal polymerization, for example known catalyst such as peroxide, for example benzoyl peroxide, chloro benzoyl peroxide, diisopropyl peroxy carbonates, two-2-ethylhexyl peroxy carbonates, t-butyl peroxy pivalate or t-butyl peroxy (2 ethyl hexanoic acid ester) or azo-compound azodiisobutyronitrile for example.The consumption of polymerization catalyst is generally 0.01-5 weight % based on the total amount of mixture.In thermal polymerization, heating-up temperature is generally 40-200 ℃ and be typically about 3 minutes to about 8 hours heating time.Except thermal polymerization, can also use the light polymerization process that utilizes Photoepolymerizationinitiater initiater or sensitizer.
[solvent]
Can dissolve or disperse in the solvent of these components dissolving by known method therein or disperse aforesaid infrared ray absorbing dyestuff, transparent resin etc. can obtain to be used for the composition of infrared ray shielding layer.The example of described solvent comprises methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, acetone, acetonitrile, carrene, dimethyl formamide, butyl acetate, toluene etc.Can suitably use in them the mixture of any or they.
With the aqueous solution rather than be dissolved in form coating water-soluble dye in the organic solvent for example in the situation of indolenine cyanines or oxole barbiturates salt dyestuff, can for example gelatin or polyvinyl alcohol be used the aqueous solution that comprises these water-soluble dyes with water-soluble polymer.
(2) adhesive layer
Advance shooting that filter, display panels, plasma display, other image show representatives such as Glat plate, CCD with under the situation of semiconductor integrated circuit, preferably by the bonding electromagnetic shielding film of the present invention of adhesive layer integrated.
In the present invention, preferably use the adhesive of refractive index 1.40-1.70.This is because by making adhesive and the refringence minimum between transparent base such as the plastic film used among the present invention can prevent that visible light transmissivity from reducing.As long as refractive index is in the scope of 1.40-1.70, visible light transmissivity descends hardly, therefore can obtain good result.
The preferred use by the heating or the flowable adhesive that pressurizes.Especially preferably when being heated to 200 ℃ or lower or at 1kgf/cm 2Or show mobile adhesive during bigger down pressurization.By using this adhesive, adhesive layer can be flowed, thereby the film with light-transmitting electromagnetic shield property is adhered on adherend such as display or the plastic plate.Owing to can flow, adhesive layer can easily make film and adherend with light-transmitting electromagnetic shield property bonding by laminated, press molding, especially, and press molding even can be bonding with adherend with curved surface or complicated shape.For this reason, preferably the softening point of adhesive is 200 ℃ or lower.Because under the environment of the film with light-transmitting electromagnetic shield property through being commonly used in temperature and being lower than 80 ℃, therefore preferably the softening point of adhesive is 80 ℃ or higher, considers most preferably 80-120 ℃ of processability.Term " softening point " refers to that viscosity becomes 10 12P or lower temperature.Under this temperature, the viscosity of material is reduced to 10 12P (10 13Pas or lower).Under this temperature, material became and can flow in about 1 to about 10 seconds usually.
List above-mentioned below by heating or the pressurization representation example of the adhesive that comprises thermoplastic resin that can flow that becomes.Promptly, can use natural rubber (refractive index n=1.52), polyisoprene (n=1.521), poly--1,2-butadiene (n=1.50), polyisobutene (n=1.505-1.51), polybutene (n=1.513), diene, as poly--2-heptyl-1,3-butadiene (n=1.50), poly--the 2-tert-butyl group-1,3-butadiene (n=1.506) and poly--1,3-butadiene (n=1.515), polyoxyethylene (n=1.456), polyoxypropylene (n=1.450), polyethers, as polyvinyl ethylether (n=1.454), polyvinyl hexyl ether (n=1.459) and polyvinyl butyl ether (n=1.456), polyester, as polyvinyl acetate (n=1.467) and polyvinyl proprionate (n=1.467), polyurethane (n=1.5-1.6), ethyl cellulose (n=1.479), polyvinyl chloride (n=1.54-1.55), polyacrylonitrile (n=1.52), polymethacrylonitrile (n=1.52), polysulfones (n=1.633), polysulfide (n=1.6), phenoxy resin (n=1.5-1.6), poly-(methyl) acrylate, as polyethyl acrylate (n=1.469), butyl polyacrylate (n=1.466), polyacrylic acid 2-ethylhexyl (n=1.463), the polyacrylic acid tert-butyl ester (n=1.464), polyacrylic acid 3-ethoxycarbonyl propyl ester (n=1.465), polyoxy carbonyl tetramethylene (polyoxycarbonyl tetramethylene) (n=1.465), polymethyl acrylate (n=1.472-1.480), polyisopropyl methacrylate (n=1.473), polymethylacrylic acid dodecane ester (n=1.474), polymethylacrylic acid tetradecane ester (n=1.475), poly-n-propyl methacrylate (n=1.484), polymethylacrylic acid 3,3,5-3-methyl cyclohexanol ester (n=1.484), polyethyl methacrylate (n=1.485), polymethylacrylic acid 2-nitro-2-methyl propyl ester (n=1.487), polymethylacrylic acid 1,1-diethyl propyl ester (n=1.489) and polymethyl methacrylate (n=1.489).When needed, two or more in can these acryloyl group polymer of copolymerization.Can also use its two or more blend.
As the resin that obtains by the resin outside copolymer acrylate resin and the acrylate, can also use epoxy acrylate (n=1.48-1.60), urethane acrylate (n=1.5-1.6), polyether acrylate (n=1.48-1.49), polyester acrylate (n=1.48-1.54) etc.From fusible viewpoint, urethane acrylate, epoxy acrylate and polyether acrylate are very excellent.The example of epoxy acrylate comprises 1, (methyl) acrylic acid addition product of 6-hexylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether, resorcinol diglycidyl ether, diglycidyl adipate ester, diglycidyl phthalate, polyethylene glycol diglycidyl ether, trimethylolpropane tris glycidyl ether, glycerine triglycidyl group ether, pentaerythrite four glycidyl group ether, D-sorbite four glycidyl group ether etc.The polymer such as the epoxy acrylate that have hydroxyl in molecule are effective for improving adhesiveness.When needed, two or more of these copolymer resins can use together.From the viewpoint of handling property, suitably be 200 ℃ or lower as the softening point of the polymer of adhesive, preferred 150 ℃ or lower.Because under the environment of electromagnetic wave shielding binder film through being commonly used in temperature and being lower than 80 ℃, therefore consider processability most preferably the softening point of adhesive be 80-120 ℃.On the other hand, preferably use weight average molecular weight be 500 or bigger polymer (use polystyrene as standard, use the value of the calibrating curve measuring that obtains by the gelatin permeation chromatography; Below identical).Molecular weight only can make adhesive composition have inadequate bonding force less than 500 polymer, and this may reduce the adhesiveness to adherend.When needed, the adhesive that the present invention uses can contain additive, as diluent, plasticizer, antioxidant, filler, colouring agent, ultra-violet absorber or tackifier.The thickness of adhesive layer is preferably about 5 to about 50 μ m, is preferably about 1 especially to about 20 μ m.
The adhesive and the refringence between the transparent plastic substrate that preferably will be coated with geometrical pattern are adjusted to 0.14 or littler.Transparent plastic substrate by adhesive layer under situation laminated on the electric conducting material, adhesive layer and the coating geometrical pattern adhesive between refringence be adjusted to 0.14 or littler.This is because when the refractive index of the refractive index of transparent plastic substrate and adhesive layer or adhesive and adhesive layer had a great difference, visible light transmissivity reduced.As long as refringence is 0.14 or littler, visible light transmissivity descends hardly, therefore can obtain good result.Using under the situation of PETG (refractive index n=1.575) as transparent plastic substrate, as the adhesive material that satisfies above-mentioned requirements, can use epoxy resin (refractive index: 1.55-1.60), as bisphenol A type epoxy resin, bisphenol f type epoxy resin, tetrahydroxyphenyl methane type epoxy resins, novolac epoxy resin, resorcinol type epoxy resin, polyalcohol polyglycols type epoxy resin, polyolefin-type epoxy resin, alicyclic or halogenated bisphenol etc.Example outside the epoxy resin comprises natural rubber (n=1.52), polyisoprene (n=1.521), poly--1,2-butadiene (n=1.50), polyisobutene (n=1.505-1.51), polybutene (n=1.5125), diene, as poly--2-heptyl-1,3-butadiene (n=1.50), poly--the 2-tert-butyl group-1,3-butadiene (n=1.506) and poly--1,3-butadiene (n=1.5 1 5), polyoxyethylene (n=1.4563), polyoxypropylene (n=1.495), polyethers, as polyvinyl ethylether (n=1.454), polyvinyl hexyl ether (n=1.4591) and polyvinyl butyl ether (n=1.4563), polyester, as polyvinyl acetate (n=1.4665) and polyvinyl proprionate (n=1.4665), polyurethane (n=1.5-1.6), ethyl cellulose (n=1.479), polyvinyl chloride (n=1.54-1.55), polyacrylonitrile (n=1.52), polymethacrylonitrile (n=1.52), polysulfones (n=1.633), polysulfide (n=1.6), phenoxy resin (n=1.5-1.6) etc.This material can show suitable visible light transmissivity.
Using under the situation of acrylate as transparent plastic substrate, except above-mentioned resin, can use poly-(methyl) acrylate, as polyacrylate ethyl ester (n=1.4685), butyl polyacrylate (n=1.466), polyacrylic acid 2-ethylhexyl (n=1.463), the polyacrylic acid tert-butyl ester (n=1.4638), polyacrylic acid 3-ethoxycarbonyl propyl ester (n=1.465), polyoxy carbonyl tetramethyl acrylate (n=1.465), polymethyl acrylate (n=1.472-1.480), polyisopropyl methacrylate (n=1.4728), polymethylacrylic acid dodecane ester (n=1.474), polymethylacrylic acid tetradecane ester (n=1.4746), poly-n-propyl methacrylate (n=1.484), polymethylacrylic acid 3,3,5-3-methyl cyclohexanol ester (n=1.484), polyethyl methacrylate (n=1.485), polymethylacrylic acid 2-nitro-2-methyl propyl ester (n=1.4868), polymethylacrylic acid four carbonyl esters (n=1.4889), polymethylacrylic acid 1,1-diethyl propyl ester (n=1.4889) and polymethyl methacrylate (n=1.489).When needed, two or more in can these acryloyl group polymer of copolymerization.Can also use two or more blend.
As the resin that obtains by the resin outside copolymer acrylate resin and the acrylate, can also use epoxy acrylate, urethane acrylate, polyether acrylate, polyester acrylate etc.From fusible viewpoint, epoxy acrylate and polyether acrylate are very excellent.The example of epoxy acrylate comprises 1, (methyl) acrylic acid addition product of 6-hexylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether, resorcinol diglycidyl ether, diglycidyl adipate ester, diglycidyl phthalate, polyethylene glycol diglycidyl ether, trimethylolpropane tris glycidyl ether, glycerine triglycidyl group ether, pentaerythrite four glycidyl group ether, D-sorbite four glycidyl group ether etc.Owing in molecule, have hydroxyl, so epoxy acrylate is effective for improving adhesiveness.When needed, two or more of these copolymer resins can use together.As the main component of adhesive, can use weight average molecular weight is 1,000 or bigger polymer.When molecular weight less than 1,000 o'clock, adhesive only has inadequate bonding force, this can reduce the adhesiveness to adherend.
Curing agent as adhesive, can use amine, as trien, dimethylphenylene diamine and diaminodiphenyl-methane, acid anhydrides, as phthalic anhydride, maleic anhydride, dodecyl succinic anhydride, equal four benzoic anhydrides and benzophenone tetracarboxylic anhydride, diamino diphenyl sulfone, three (dimethylaminomethyl) phenol, polyamide, dicyano diamides, ethyl-methyl imidazoles etc.Can use one or both or multiple mixture in these curing agents.By the above-mentioned polymer of 100 weight portions, the amount of crosslinking agent is the 0.1-50 weight portion, preferred 1-30 weight portion.When curing agent addition during less than 0.1 weight portion, it is insufficient to harden.On the other hand, when its amount surpasses 50 weight portions, can cause excessively crosslinkedly, sometimes adhesiveness be had adverse effect.When needed, the resin combination that is used as adhesive of the present invention can contain additive, as diluent, plasticizer, antioxidant, filler or tackifier.Be coated with this resin combination as adhesive, make coating completely or partially constitute base material, described base material has the geometrical pattern of drawing with electric conducting material on the transparent plastic substrate surface.After solvent evaporated and the heat hardening, obtain adhesive film of the present invention.The adhesive film that obtains like this has electromagnetic wave shielding performance and transparency, and owing to contained adhesive in the adhesive film, is directly bonded on CRT, PDP, liquid crystal or the EL display.Selectively, it is adhered to plate or sheet such as acrylate plate or glass plate, is used for display then.Can also use this adhesive film with above-mentioned same way as in the hole of inside that is used for observing the measurement mechanism, measuring instrument or the manufacturing installation that generate electromagnetic waves or housing.In addition, can also be used in and have by in the building window of the electromagnetic interference danger of electric wave tower or high-voltage line, the automobile window etc.Preferably the geometrical pattern of drawing with electric conducting material has earth connection.
Removed the part on the transparent plastic substrate surface of electric conducting material, deliberately formed peak and paddy, perhaps the back side pattern of electric conducting material has been transferred on it.Therefore, lip-deep light scattering reduces transparency.By being coated with face smoothly near the resin of transparent plastic substrate, thereby make irregular reflection minimum and show transparency, can overcome this problem with peak and paddy with refractive index.Because live width is minimum, therefore the geometrical pattern of drawing on transparent plastic substrate with electric conducting material with the naked eye can not be seen.In addition, enough big at interval, this seems and helps to show obvious transparency.On the other hand, the interval of geometrical pattern is little more a lot of than the electromagnetic wavelength that is blocked, and this also seems and helps to show transparency.
Shown in JP-A-2003-188576, being laminated under the situation on the metal forming individually or with transparent plastic substrate that the laminated thing of another kind of resin constitutes, can under the situation that does not form adhesive layer, carry out laminated by film with high hot melt ethylene-vinyl acetate copolymer resin or high hot-melt resin such as ionomer resin.Yet commonly used is that the dry laminating method of use adhesive layer etc. carries out laminated.The example that constitutes the adhesive of adhesive layer comprises the adhesive that contains acrylate, mylar, polyurethane resin, polyvinyl alcohol resin, vinyl chloride/vinyl acetate copolymer resin, ethylene resin etc.In addition, can use thermosetting resin or ionizing ray-hardening resin (ultraviolet hardening resin, electron beam-hardening resin etc.).
Because display has glass surface usually, thereby use contact adhesive that transparent plastic film is adhered on the glass plate.Therefore, produce variety of issue, bubble or peel off, and make anamorphose or by inherent colour generation look change to be shown as adhesive surface.The foaming and the problem of peeling off cause from peeling off of plastic film or glass plate by contact adhesive.This phenomenon may appear at plastic film side and glass plate side.Promptly appear at the less side of bonding force.Therefore, contact adhesive is at high temperature tackled plastic film and glass plate all has bigger bonding force.More specifically, preferably contact adhesive bonding force to plastic film and glass plate under 80 ℃ is 10g/cm or bigger, more preferably 30g/cm or bigger.Yet, do not need sometimes to use bonding force to surpass the contact adhesive of 2000g/cm, because adhesion process becomes numerous and diverse in this case, although do not having can to use this contact adhesive without any problem ground under the situation of above-mentioned trouble.Can also not be provided in the face of transparent plastic film one side has the contact adhesive part of paper (dividing plate), thereby prevent and unessential the contacting of other parts.
The preferred transparent pressure sensitive adhesive that uses.More specifically, the total light transmittance of contact adhesive is preferably 70% or higher, and more preferably 80% or higher, 85-92% most preferably.Further preferably contact adhesive has low haze.More specifically, the mist degree of contact adhesive is preferably 0-3%, more preferably 0-1.5%.For preventing to become from inherent colour generation look to be shown, preferably the contact adhesive of the present invention's use is colourless.Yet it is colourless basically that the contact adhesive with less thickness is construed to basically, although resin itself is coloured.In addition, the deliberately painted situation of aftermentioned is not in this scope.
Example with contact adhesive of above-mentioned characteristic comprises acryloyl group-Ji resin, alpha-olefin resin, vinyl acetate-Ji resin, acrylate copolymer-Ji resin, carbamate-Ji resin, epoxy-Ji resin, vinylidene chloride-Ji resin, ethane-acetic acid ethyenyl ester-Ji resin, polyamide-Ji resin, polyester-Ji resin etc.Wherein, acryloyl group-Ji resin is preferred.Even under the situation of using a kind of resin,, also can improve pressure-sensitive-adhesive by for example being reduced in end group with addition, adding tackify composition or the modification molecule of crosslinking agent in the synthetic contact adhesive of polymerization.In addition, even under the situation of using a kind of contact adhesive, the face bonding by for example surface modification transparent plastic film or glass plate and contact adhesive also can improve adhesiveness.The example of surface modifying method comprises physical process, handles as corona discharge and plasma aura, and is formed for improving fusible priming coat.
From the viewpoint of transparency, colourless property and handling property, preferably the thickness of pressure sensitive adhesive layer is the about 50 μ m of about 5-.Using adhesive to form under the situation of pressure sensitive adhesive layer, thickness can reduce in above-mentioned scope, more specifically, is the about 20 μ m of about 1-.Yet, Show Color itself not being changed and obtaining under the situation of the transparency in the above-mentioned scope, layer thickness can exceed the above-mentioned upper limit.
(3) comprise the antistatic agent of inorganic oxide
The layer that preferably comprises the layer of infrared ray absorbing dyestuff or be in contact with it comprises the antistatic agent that contains inorganic oxide.This is because can prevent thus because static causes being not intended to form the argent part by development treatment.
As inorganic oxide, conducting metal oxide is preferred.
As conductive metal oxide particle, needle-shaped particles is preferred.Preferably use the ratio (major axis/minor axis) of major axis and minor axis to be 3-50, the needle-shaped particles of preferred especially 10-50.The minor axis of preferred these needle-shaped particles drops in the 0.001-0.1 μ m, the particularly scope of 0.01-0.02 μ m.Also preferred its major axis drops in the 0.1-5.0 μ m, the particularly scope of 0.1-2.0 μ m.
The example of the material of aforesaid conductive metal oxide particle comprises ZnO, TiO 2, SnO 2, Al 2O 3, In 2O 3, MgO, BaO and MoO 3, they composite oxides and comprise the metal oxide of these metal oxides with hetero-atom.As metal oxide, SnO 2, ZnO, Al 2O 3, TiO 2, In 2O 3With MgO be preferred, SnO 2, ZnO, In 2O 3And TiO 2Be more preferably and SnO 2Be particularly preferred.As the example that comprises a small amount of heteroatomic metal oxide, can exemplify ZnO, the Nb-of Al-or In-doping or the TiO that Ta-mixes 2, the In that mixes of Sn- 2O 3SnO with Sb-, Nb-or halogen doping 2, have the hetero-atom of 0.01-30 mole % (preferred 0.1-10 mole %) separately.When heteroatomic addition during, can not give composite metal oxide sufficient conductivity less than 0.01 mole of %.When its amount surpassed 30 moles of %, the melanism degree of particle improved and antistatic layer (layer that comprises antistatic agent) blackening, and this is not suitable as silver sensitive material.Therefore, preferred in the present invention the use comprises a small amount of heteroatomic metal oxide or the composite metal oxide material as conductive metal oxide particle.In addition, the metal oxide that has oxygen defect in its crystal structure is preferred.As comprising a small amount of heteroatomic conductive metal oxide particle, the SnO that preferred antimony mixes 2Particle and the SnO that especially preferably mixes with 0.2-2.0 mole % antimony 2Particle.In order to form antistatic layer, advantageously use metal oxide with aforesaid minor axis length and long axis length (SnO that mixes of antimony for example in the present invention with high transparency and favourable conductivity 2) particle.Therefore, can easily obtain to have mist degree be 3% or the surface resistivity of littler and superficial layer be 8 * 10 6To 6 * 10 8The silver sensitive material of the support that static is not too arranged of Ω.
Use the aciculiform metal oxide (SnO of antimony doping for example of short and major axis dimension such as top appointment 2) as if to advantageously generate the reason of the antistatic layer with the high grade of transparency and favourable conductivity as follows for particle.In antistatic layer, these aciculiform metal oxide particles stretch with the long axis direction parallel with the antistatic layer surface, and these particles only occupy the space corresponding to the minor axis diameter on thickness direction.Because stretch along long axis direction as mentioned above, these aciculiform metal oxide particles contact with each other with the frequency higher than normally used spheric granules.Therefore, even also can realize high conductivity on a small quantity.Therefore, transparency decline low surface resistivity can not damaged.In aforesaid aciculiform metal oxide particle, the minor axis diameter usually less than or almost the thickness with antistatic layer is identical.Therefore, these particles are outstanding seldom from the teeth outwards.If there is outstanding situation, outstanding is that superficial layer very little and that therefore almost formed on antistatic layer covers fully.The result brings another advantage: be used for the process of silver sensitive material support or at rare ash of process (promptly protrusion comes off in the layer) of the photosensitive material that conveying is used for exposing or develops in conveying.In the situation of spheric granules, silver sensitive material surface resistivity change before development treatment and afterwards bigger.In contrast, in the situation of using aforesaid aciculiform metal oxide particle, observe extreme variation.Therefore, we can say and improved the transport property after the development treatment greatly.This is seemingly because in spheric granules and since the expansion of the film that development treatment causes or shrink changed to a greater degree orientation and therefore intergranular contact area become less than the area in the needle-shaped particles.
Preferably be used for disperseing and keep the form coating of mixture of the binding agent of conductive metal oxide particle to be used for the present invention's antistatic agent.As the material of binding agent, can use various polymer for example acrylic resin, vinylite, polyurethane resin and mylar.From preventing the angle of ash, preferred described binding agent is the hardening product that comprises polymer (preferred acrylate copolymer, polyvinyl, polyether polyols with reduced unsaturation or polyester polymers) and carbodiimide compound.From keeping favourable operational environment and prevent the air-polluting angle, preferred in the present invention described polymer and carbodiimide compound all are water miscible or to be dispersed in the state in the water, use as emulsion.For can be crosslinked with carbodiimide compound, polymer has methylol, hydroxyl, carboxyl and amino.Wherein, hydroxyl and carboxyl are preferred and carboxyl is particularly preferred.The hydroxyl that comprises in the polymer or the amount of carboxyl are preferably 0.0001 to 1eq./kg, and preferred especially 0.001 to 1eq./kg.
The amount of the inorganic oxide that comprises in the antistatic layer is preferably 1-95 weight %, more preferably 5-85 weight %, and more preferably 10-70 weight %.
(4) strippable protective film
Light-transmitting electromagnetic screened film of the present invention can provide protective film.
This protective film always is not provided on the two sides of electromagnetic shielding film (light-transmitting electromagnetic screened film).Also promptly protective film only can also be located on the net-shaped conductive metal part, and not be located at transparent basement membrane side (that is, corresponding to " transparent support ") referred in this.Protective film only can also be provided at transparent basement membrane side, and not be located in the conducting metal portion.
When being used for aforesaid filter, display panels, plasma display etc., by adhesive layer bonding electromagnetic shielding film.Therefore, should in laminated step, peel off aforesaid protective film.Therefore, preferably with the strippable mode of what is called laminated protective film on electromagnetic shielding film.
The peel strength of protective film is preferably the 5mN/25mm width to the 5N/25mm width, and more preferably the 10mN/25mm width is to the 100mN/25mm width.It is undesirable that peel strength is lower than above-mentioned lower limit, be easy to very much take place because peel off, therefore, in this case in processing or owing to involuntary contact may be peeled off protective film.In addition, it is undesirable that peel strength surpasses the above-mentioned upper limit, because need bigger power to peel off, the net-shaped conductive metal part is separated with transparent basement membrane (or adhesive layer).
Preferably can tolerate and develop and the plating condition at the laminated protective film of transparent basement membrane side.Promptly preferably protective film can not peeled off after these are handled yet and can not pollute.
In order to satisfy above-mentioned requirements; as the film that constitutes protective film, the preferred resin film that constitutes by vistanex such as polyvinyl resin or acrylic resin, mylar such as pet resin, polycarbonate resin, acrylate etc. that uses.From the point of view, further preferably, when being used for laminated thing, the one side at least that is used as outmost protective film has stood Corona discharge Treatment, or forms adhesion-promoting layer thereon.
Contact adhesive as constituting protective film can use acrylate-Ji, rubber-Ji or polysiloxanes-based pressure-sensitive adhesive.
The thin-film material of protective film and used in pressure sensitive adhesive also is applicable to the protective film of using in the conductive metal layer side.Therefore, as these protective films, can use different films or identical film.
(5) melanism layer
Light-transmitting electromagnetic screened film according to the present invention can stand melanism to be handled.
Melanism is handled for example open by JP-A-2003-188576.Handle the melanism layer that forms by described melanism and can give rust inhibition and antireflection character.For example can suppress the reflection on the metal foil surface by the melanism layer that the Co-Cu alloy plating forms.In addition, can carry out chromate thereon handles as antirust processing.By contain chromate or bichromate as the solution of main component in the impregnate layer compound, dry carry out chromate and handle to form anti-rust coating.When needed, can carry out chromate on the one or both sides of metal forming handles.Can form the melanism layer by electro-plating method, thereby obtain black coating film.For example, can form this layer by the compound that uses nickel (Ni), zinc (zn) or tin (Sn).Selectively, by using for example electrodepositable coating material of electrodepositable ionic polymers material can form this layer.
As the electrolyte bath that comprises aforesaid melanism material (black plating bath), can use in the present invention and contain the black electroplating bath of nickelous sulfate as main component.In addition, can use commercially available black electroplating bath.Object lesson comprises Shimizu Co. as used herein, black electroplating bath (the NOBUROI SNC that Ltd. makes TM, the Sn-Ni alloy-based), NIHON KAGAKUSANGYO Co., black electroplating bath (the NIKKA BLACK that Ltd. makes TM, the Sn-Ni alloy-based), black electroplating bath (the EBONY CHROM that KINZOKU KAGAKU KOGYO K.K. makes TM85SERIES, the Cr yl) etc.
In the situation of the metal level that so forms electro-deposition, can use this area electrolytic etching of metal matter technology commonly used.Because multiple cheap metal electrolyte is arranged, advantageously can freely select to be suitable for the electrolytic etching of metal matter of purpose.
At for example metallide metal is in the situation of Cu, by using hydrogen sulfide (H 2S) solution surface is handled and can be made Cu surface melanism.
In the present invention, by using sulfide-based compound can easily prepare black agent.Selectively, for example COPPER BLACK of multiple commercially available inorganic agent is arranged TMCuO, COPPER BLACK TMCuS, selenium-Ji COPPER BLACK No.65 etc. (producing) and EBONOL CSPECIAL by ISOLATE KAGAKU KENKYUSHO TM(being produced by MELTEX Inc.) also can be used for the present invention.
(6) other functional layer
In the present invention, can also form functional layer separately if desired with various functions.Can have various performances according to the described functional layer of purpose.For example, anti-reflection layer with anti-reflective function is provided for the electromagnetic shielding material that is used for display by control refractive index and thickness, non-glare layer or antiglare layer (both all have anti-dazzle function), in the limited wavelength zone, can absorb the tone key-course of visible light, stain-proofing layer with the function of removing pollutions such as fingerprint easily, prevent the hard conating of polishing scratch, can absorb the layer of bang, can when breaking, prevent layer that sheet glass is scattered etc.These functional layers can form on the opposite face of the argentiferous salt deposit that passes support or can form on identical faces.
These functional layers can directly bond with PDP.Selectively, these layers can be bonded to the plasma display body portion from transparent support for example on glass plate or the acrylic resin board.The functional membrane that so constitutes is called optical light filter (perhaps only being called filter).
(antireflection and anti-dazzle character)
Preferably the light-transmitting electromagnetic screened film has antireflection (AR character, antireflection and anti-dazzle (ARAG) character of satisfying two kinds of demands of preventing anti-dazzle (AG) character of direct reflection or giving it of the external light reflection of preventing.
Owing to these performances, can overcome the problem of the observation of the external image disruption display screen that reflection by lighting apparatus etc. causes.By reducing the visible reflectance on film surface, not only can prevent external light reflection but also can improve contrast etc.In the situation of the bonding antireflection of light-transmitting electromagnetic screened film/anti-dazzle functional membrane, the visible light refractive index is preferably 2% or littler, and more preferably 1.3% or littler and more preferably 0.8% or littler.
Aforesaid functional membrane can form by antireflection/anti-dazzle functional layer is provided on suitable transparent substrates.
Anti-reflection layer can be prepared as follows: prepare with for example individual layer of 1/4 wavelength optical film thickness by forming the film be made of transparent fluoropolymer resin, magnesium fluoride, polysiloxanes-Ji resin or silica, perhaps the multilayer by the laminated film that has different refractivity and be made of inorganic compound such as metal oxide, fluoride, silicide, nitride or sulfide or organic compound such as polysiloxanes-Ji resin, acrylate or fluoride resin prepares.
Have about 0.1 μ m on the use surface and can form antiglare layer to the little peak of about 10 μ m and the antiglare layer of paddy.More particularly, by in thermosetting or light-cured resin such as acrylate, polysiloxanes-Ji resin, melamine-Ji resin, carbamate-Ji resin, alkyd resins-Ji resin or fluoride resin, disperseing the particle of inorganic compound or organic compound such as silicon dioxide, organo-silicon compound, melamine or acrylate to obtain printing ink, then printing ink is coated on the base material, reharden, thereby make this function film.
The average diameter of particle is preferably the about 40 μ m of about 1-.
Selectively, by coated heat solidity or photo-curable resin,, can form antiglare layer having the mould compacting sclerosis then of required gloss or surface state.
After forming antiglare layer, the mist degree of light-transmitting electromagnetic screened film is 0.5% or bigger but be not more than 20%, preferred 1% or bigger but be not more than 10%.When mist degree is too low, only can obtain not enough anti-dazzle character.On the other hand, under very high mist degree, the definition of transmission image (sharpness) is tended to descend.
(hard conating character)
For giving the light-transmitting electromagnetic screened film enough marresistances, preferably function film has and is coated with performance firmly.By for example using thermosetting or light-cured resin such as acrylate, polysiloxanes-Ji resin, melamine-Ji resin, carbamate-Ji resin, alkyd resins-Ji resin or fluoride resin can form hard-coated film, but material and formation method are not particularly limited.The thickness of hard conating is preferably the about 50 μ m of about 1-.Preferably on hard conating, form anti-reflecting layer and/or antiglare layer, because can obtain having the function film of marresistance, antireflective property and/or anti-dazzle performance like this.
Consider the case hardness of it being given the light-transmitting electromagnetic screened film that is coated with character firmly, its pencil intensity definite according to JIS (K-5400) preferably is at least H, more preferably 2H or more than, and more preferably 3H or more than.
(anti-static function)
Because the dust that electrostatic charge or discharge cause and the adhesion of fragment, preferred light-transmitting electromagnetic screened film has anti-static function in order to prevent when contacting with human body.
As functional membrane with anti-static function, can use to have high conductivity, for example be expressed as about 10 with surface resistivity 11Ω/ or lower functional membrane.
By on transparent substrates, forming the film that antistatic layer can obtain to have high conductivity.The instantiation that can be used for the antistatic agent in the antistatic layer comprises PELLESTAT TM(by SANYO CHEMICAL INDUSTRIES, Ltd. produces), ELECTROSLIPPER TM(producing) etc. by KAO.Can also by use with ITO as the known nesa coating of representative or wherein be dispersed with electrically conductive particles for example the conducting film of ITO particulate or tin oxide particulate form antistatic layer.Can also give anti-static function to give hard conating, anti-reflection layer or antiglare layer by for example adding electrically conductive particles.
(antifouling character)
Preferably the light-transmitting electromagnetic screened film has soil resistance, because can prevent dirts such as fingerprint, and when dirt is arranged, also can easily remove.
For example, by on transparent substrates, providing anti-fouling compound can obtain to have the functional membrane of antifouling character.As anti-fouling compound, can use water and/or fat and the oily material that does not have wetting property, for example fluorine compounds or silicon compound.The instantiation of fluorine-containing anti-fouling agent comprises OPTOOL TM(by DAIKIN INDUSTRIES, Ltd. produces) etc., and the instantiation of silicon compound comprises TAKATAQUANTUM TM(producing) etc. by NOF company.
(ultraviolet screener character)
For the dyestuff and the transparent substrates deterioration that prevent from will be described below, preferably the light-transmitting electromagnetic screened film has ultraviolet screener character.By adding ultra-violet absorber to transparent substrates itself or it being formed the described functional membrane that UV-absorbing layer can obtain to have ultraviolet screener character.
In order to cut off ultraviolet ray, be shorter than light transmittance in the ultra-violet (UV) band of 380nm at wavelength and should be 20% or littler, preferred 10% or littler and more preferably 5% or littler with the protection dyestuff.Can obtain to cut off ultraviolet functional membrane by on transparent substrates, forming the layer comprise ultra-violet absorber or reflection or to absorb ultraviolet inorganic compound.As described ultra-violet absorber, can use known absorbent for example BTA or benzophenone.Wait to determine its kind and concentration according to the dispersibility in medium to be dispersed or dissolved or solubility, absorbing wavelength, absorption coefficient, dielectric thickness, be not particularly limited.
Preferably can cut off ultraviolet functional membrane has little absorption and can not cause the big decline of visible light transmissivity and can not cause painted for example flavescence at visible region.
Form in described functional membrane in the situation of the layer that contains dyestuff that will be described below, preferably the outside that layer is positioned at this layer is cut off in ultraviolet ray.
(gas barrier character)
When the light-transmitting electromagnetic screened film is used for temperature and is higher than room temperature or humidity and is higher than the environment of common humidity, observe sometimes owing to moisture occurs and make aftermentioned dyestuff deterioration, or since in the adhesive of bonding usefulness or the gathering of adhesive interface place moisture become turbid.Therefore, preferably the light-transmitting electromagnetic screened film has capacity for air resistance.
For preventing dyestuff sex change or muddiness, should prevent that water intrusion from containing in the layer or adhesive phase of dyestuff.For this reason, preferably the vapour transmission degree of light-transmitting electromagnetic screened film is 10g/m 2. sky or littler, preferred 5g/m 2. sky or littler.
(other optical characteristics)
The light-transmitting electromagnetic screened film is being used in the situation of plasma scope, preferably its transmitted colors is neutral gray or pewter.This is because must keep or improve the characteristics of luminescence and the contrast of plasma scope, and is preferred than the white of the slightly higher colour temperature of reference white in some cases.It is believed that the color reprodubility of colour plasma display is insufficient.Therefore, preferably, optionally reduce the unwanted luminous of the fluorophor cause the problems referred to above or emission gases.Especially, the luminous spectrum in the red display shows several emission peaks in the about 700nm of the about 580nm-of wave-length coverage, and the problem that causes is, because in short wavelength side stronger emission relatively, makes low orange of emitting red light advancing color purity.Use dyestuff can control these optical characteristics.Promptly use near infrared absorbent can cut off near infrared ray, use can optionally absorb unwanted luminous dyestuff can reduce unwanted luminous, thereby obtain required optical characteristics.Use has the dyestuff of suitable absorption in the visual field, can make the tone of filter good.
Use one or more to be selected from following method and can comprise dyestuff: use by mediating thin polymer film or the resin plate that one or more dyestuffs and transparent resin are made (1); (2) use by in comprising the dense resin solution of resin monomer/organic solvent, dispersing or dissolving thin polymer film or the resin plate that one or more dyestuffs are made through casting method; (3) use by one or more dyestuffs and resinoid bond being added to the thin polymer film or the resin plate of the coating coating that obtains in the organic solvent; (4) use the transparent pressure sensitive adhesive that contains one or more dyestuffs; But the invention is not restricted to this.In this specification, term " comprise " not only refer to be contained in base material, the layer as film or contact adhesive in, and be coated on base material or the layer the surface on.
Above-mentioned dyestuff can be common dyes or the pigment that has required absorbing wavelength in the visual field, and its kind is not particularly limited.Its example comprises general commercially available organic dyestuff, as anthraquinone, phthalocyanine, methine (methine), azomethine, oxazine, imonium, azo, styrene base class, cumarin, porphyline, dibenzofurans, diketopyrrolopyrroles, rhodamine, xanthene, pyrroles's methine (pyrromethene), two mercaptan and diimonium compound.Medium that the kind of dyestuff and concentration are disperseed therein according to the required through performance of the absorbing wavelength of dyestuff and absorption coefficient, filter and transmitance and dyestuff or the kind of filming and thickness are determined, have no particular limits.
Have high surface temperature and the plasma display that is used for high ambient temperature, the filter temperature also raises.Therefore, preferably the thermal endurance of dyestuff can be because of for example not decomposing serious deterioration down at 80 ℃.Except thermal endurance, some dyestuffs lack light resistance.Ultraviolet light or visible light in the luminous or exterior light of plasma display cause the deterioration problem, use contains the element of ultra-violet absorber or ultraviolet ray-blocking element or uses not the dyestuff that can cause serious deterioration because of ultraviolet light or visible light, alleviates because of ultraviolet light to make the dyestuff deterioration.Except light and heat, be suitable for too for humidity and environment with these factors combine.When the dyestuff deterioration, display filter see through characteristic variations, so its tone variations, or the ability drop of block near infrared line.Because during dyestuff will be dispersed in medium or films, therefore solubility or the dispersiveness in sufficient solvent also was key factor.In the present invention, during two or more dyestuffs with different absorbing wavelength can be contained in single medium or film.Can also provide and contain two or more and contain the medium of dyestuff or film.
Some dyestuffs can because of with the Metal Contact deterioration.In using the situation of this dyestuff, more preferably in comprising the functional membrane of described dyestuff, with not with the light-transmitting electromagnetic screened film in argent part or the mode that partly contacts of conducting metal arrange the layer that contains dyestuff.
For the ability of the shielding electromagnetic wave that prevents the light-transmitting electromagnetic screened film reduces, preferably make argent part or conducting metal partial earthing.Promptly preferably on the light-transmitting electromagnetic screened film, be formed for the current-carrying part of ground connection and this current-carrying part is contacted with the grounded part that shows body.Around argent part or conducting metal part, suitably form described current-carrying part along the light-transmitting electromagnetic screened film.
Current-carrying part can be the net-like pattern layer or the layer solid metal paper tinsel layer for example of patterning not.But, in order to realize and to show the favourable conductivity of grounded part of body, not the current-carrying part of patterning for example solid metal paper tinsel layer be preferred.
Because current-carrying part can also former state as electrode, so suitable be that current-carrying part is that for example solid metal paper tinsel and/or the current-carrying part of not patterning has sufficiently high mechanical strength.
In order to be protection current-carrying part and/or realization and the favourable conductivity of grounded part in the situation of net-like pattern layer at current-carrying part, preferably in current-carrying part, form electrode sometimes.Although the shape of this electrode is not particularly limited, the electrode that covers current-carrying part fully is preferred.
From conductivity, corrosion resistance and with the fusible viewpoint of nesa coating, the examples of material that electrode is used comprises that the metal that can use separately or use with two or more alloy is as silver, copper, nickel, aluminium, chromium, iron, zinc and carbon, the mixture of these metals (individually or alloy) and synthetic resin and comprise borosilicate glass and the pastel of the mixture of these metals (individually or alloy).For printing and being coated with this pastel, can use known method.In addition, commercially available conductive strips can suitably use.As conductive strips, can use the band that has conductivity on the two sides, or use the one-sided adhesive type of carbon dispersion type electroconductive binder.The preferred band that uses the both-sided adhesive formulation.The thickness of electrode is extremely several mm of a few μ m, but the invention is not restricted to this.
According to the present invention, can obtain having the filter of excellent optical characteristics, can keep like this or even improve the picture quality of plasma scope, and can not damage its brightness greatly.Can also obtain the filter of electromagnetic wave shielding ability excellence, the electromagnetic wave that is considered to have health adverse effect that its blocking-up produces from plasma scope, and can block the near-infrared light beam of the about 1000mn of about 800-that plasma scope produces effectively, and can adverse effect not arranged, thereby can prevent mechanical breakdown to the wavelength of uses such as peripheral unit such as Long-distance Control, transmission optical communication system.In addition, can low-cost provide the filter that has excellent weather resistance.
When having according to the film of light-transmitting electromagnetic screened film of the present invention and aforesaid functional membrane, PDP or during as the bonding glass of filter substrate, observing the intrusion bubble sometimes.In the case, can outgas or be dissolved in the bubble of invading when bonding between the parts in the contact adhesive by adding to be pressed in.
The example of pressure method comprises: be included in the method that the holding sheet compound also pressurizes between flat board, comprise and make laminated thing add the method for depressing by between the clutch roller (nip rolls), with comprise the method that places pressurizing vessel to pressurize then laminated thing, but the present invention is not specially limited in this.Method in the pressurizing vessel pressurization is preferred, because pressure can be uniformly applied on the whole laminated thing, and does not have inhomogeneities, and can handle a plurality of laminated things simultaneously.As pressurizing vessel, can use autoclave.
About pressurized conditions, can remove the intrusion bubble efficiently, and can under high pressure shorten processing.Consider the resistance to pressure of laminated thing and the restriction of pressue device, pressure is extremely about 2MPa of about 0.2MPa, and preferred 0.4 to 1.3MPa.Change with pressurized conditions pressing time, without limits.Cost is increased.Therefore, preferably under proper condition, under 6 hours or shorter time of staying, pressurize.Under the situation of using pressurizing vessel, be under predetermined pressure level, to keep about 10 minutes to about 3 hours with being particularly suitable for.
In some cases, preferably heat simultaneously in pressurization.Heating makes mobile interim increase of light transmission contact adhesive, thereby promotes the bubble degassing in the contact adhesive or promote dissolving.Depend on each element of constituting filter tolerance, can not heat to not being higher than under about 80 ℃ in room temperature, but the present invention is not particularly limited in this heat.
Pressurization or heat treated are favourable, because can improve the bonding bonding force afterwards of each element that constitutes filter.
Embodiment
Next, will illustrate in greater detail characteristic of the present invention with reference to the following examples and Comparative Examples.The material of Xian Shiing, consumption, ratio, processing, processing procedure etc. can randomly change within the scope of the invention in the following embodiments.That is to say that scope of the present invention should not be construed as limited to the following examples.
Embodiment 1
[preparation near infrared shielding film]
(being used to shield near infrared preparation of compositions)
In the solvent mixture that comprises methyl ethyl ketone and toluene (weight mixing ratio: 50: 50) dissolving and mix 2 weight portion IRG-022 and (produce by NIPPON KAYAKU, fusing point: 200 ℃), be N, N, N ', N '-four (to the diethylamino phenyl)-1,4-benzoquinone-two (imonium) hexafluoro antimonate, as Diimmonium compound as the first near-infrared absorbing dyestuff, 1 weight portion EXCOLOR810K (is produced by NIPPON SHOKUBAI, the absorption coefficient of maximum absorption wavelength with at 450nm, the ratio of the absorption maximum coefficient under 550nm and the 620nm is respectively 10.2,8.3 and 9.1), as phthalocyanine dye as the second near-infrared absorbing dyestuff, and 100 weight portion DIANAL BR-80 (produce by MITSUBISHI RAYON, glass transition temperature: 105 ℃), obtain resin combination.
(formation of near-infrared shielding)
(produced thickness by FUJI PHOTOFILM: 75 μ m), coating comprises the above-mentioned resin combination that is used for near-infrared shielding of described Diimmonium compound, obtains the thickness of 15 μ m after drying at the PET resin molding.Therefore, laminated described near-infrared shielding obtains near infrared shielding film.
[preparation of electromagnetic shielding film]
(photosensitive silve halide material)
Preparation comprise the 10.0g gelatin to 60g in water-bearing media Ag and comprise the emulsion of the iodine silver bromide that the average diameter with corresponding ball is 0.1 μ m (I=0.2 mole %, Br=40 mole %).
In this emulsion, add K 3Rh 2Br 9And K 2IrCl 6To obtain 10 -7The concentration of mol/mol Ag, thereby with Rh ion or Ir ion doping silver bromide grain.In this emulsion, add Na 2PdCl 4And use gold chloride and sodium thiosulfate to carry out gold-sulphur sensitizing.Next, near infrared shielding film, be coated with described emulsion, to obtain 1g/m with the gelatin film curing agent 2Silver-colored coating weight.In this step, the volume ratio of adjusting the Ag/ gelatin is 1/2.This emulsion is applied on the opposite face of the face that scribbles the near-infrared shielding composition.
Emulsion is coated on (25cm is wide, and 20m is long) on the wide PET support parts of 30cm.Then, under the central authorities (24cm) that keep coated portion, cut the both sides (3cm) of support, the photosensitive silve halide material that obtains curling.
(exposure)
The continuous exposure device that use is put down in writing in the embodiment of JP-A-2004-1244 makes the photosensitive silve halide material exposure, wherein use the photohead of DMD (digital mirror device) on the width of 25cm, to arrange, under the state of bending, provide photohead and exposure desk with the image focusing of laser beam to photosensitive layer, connect photosensitive material feed unit and curling unit, given deviation with cushioning effect is to prevent to curl and the influence for the speed of exposed portion of the velocity variations of feed unit.Exposure wavelength is 400nm, and beam pattern is near the square of 11 μ m, and LASER Light Source output is 100 μ j.
Expose, obtain 45 ° of grid patterns, interval 300 μ m, width 24cm, continuous length 10m.After the electroplating processes that will be described below, confirm that copper pattern has the live width of 11 μ m of 300 μ m spacings.
(development treatment)
The composition of developer solution (1L) (replenish liquid and have identical composition)
Hydroquinones 27g
Sodium sulfite 50g
Potash 40g
Ethylenediamine tetra-acetic acid 2g
KBr 3g
Macrogol 2000 1g
Potassium hydroxide 4g
PH is adjusted to 10.3
The composition of fixing solution (1L) (replenish liquid and have identical composition)
ATS (Ammonium thiosulphate) (75% solution) 300ml
Ammonium sulfite monohydrate 25g
1,3-diaminopropanetetraacetic acid ester 8g
Acetate 5g
Ammoniacal liquor (27%) 1g
PH is adjusted to 6.2
The solution that use is listed above, using under FG-710 PTS type automatic processing machine (being produced by the FUJIFILM) development conditions below makes the photosensitive material (being also referred to as the material of sensitizing) of exposure stand development treatment: develop: following 40 seconds at 25 ℃, photographic fixing: 304 ℃ following 23 seconds, washing: in following 20 seconds of the water (5L/min) that flows.
In the processing of operation, at supply 500ml/m 2Developer replenishers and 640ml/m 2Fixing solution the time, development 100m 2The photosensitive material in/sky 3 days.
Therefore, construct the film that on hyaline membrane, has grid silver net pattern.The surface resistivity of this film is 50 Ω/.
(electroplating processes)
The film that has formed silver-colored net pattern above the metallide equipment that possesses metallide groove (10) as shown in fig. 1 by use makes stands electroplating processes.Aforesaid photosensitive material is installed on the metallide equipment netted the facing down of silver (make silver netted contact with feed roller).
(12a 12b), uses to have special stainless steel rider (diameter: 10cm, the length: 70cm) of the thick electrolytic copper plating layer of 0.1mm from the teeth outwards as feed roller.As deflector roll (14) and other conveying roller, use not copper-plated roller (diameter: 10cm, length: 70cm).By adjusting the height of deflector roll (14), no matter linear velocity how, guarantees the constant processing time in electroplate liquid.
(distance L shown in Fig. 1 a) is adjusted into 10cm with the distance between bottom part of entrance side feed roller (12a) and film silver-colored netted contact-making surface and plating bath face.Distance (the distance L b shown in Fig. 1) between bottom part of silver-colored netted contact-making surface of outlet side feed roller (12b) and photosensitive material and plating bath face is adjusted into 20cm.
In electroplating processes, the composition of plating bath, the soak time (time in the solution) in each is bathed and to each bath to apply voltage as follows.Treatment fluid temperature and washing temperature all are 25 ℃.The composition of metallide liquid (replenish liquid and have same composition)
Salzburg vitriol 75g
Sulfuric acid 190g
Hydrochloric acid (35%) 0.06mL
Copper?Gleam?PCM 5mL
(producing) by Rohm and Haas Electronic Materials
Pure water is filled to 1L
Processing time in the plating bath
Washed 1 minute
Pickling 30 seconds
Electroplated 1 30 seconds
Electroplated 2 30 seconds
Electroplated 3 30 seconds
Electroplated 4 30 seconds
Washed 1 minute
Antirust processing 30 seconds
Washed 1 minute
Linear velocity with 2m/min is handled membrane sample with 10m part.Therefore, obtain electromagnetic wave shielding membrane sample 1-1, it has the uniform surface resistance rate and electroplates equably.
(preparation of comparative sample and evaluation)
For relatively, with as the silver-colored reticular membrane of the above-mentioned development (25cm * 25cm) that cuts into slices.After connecting copper electrode on the side, it is immersed in 3 minutes and copper facing under 10V voltage in the above-mentioned plating bath.Therefore, preparation comparative sample 1-2.Distance between electrode and plating bath is 10cm.
Measure the surface resistivity of plated film and estimate the uniformity of coating with bore hole.As a result, at the about 2cm width of the nearest part of distance liquid level place electroplated sample, although be immersed in the plating bath, the bottom is not electroplated yet.
According to the method for describing among the embodiment 1 of patent documentation 10 (JP-A-2004-221564), preparation has the electromagnetic shielding film of electromagnetic wave shielding character as sample 1-3.By using photomask (5cm * 5cm) carry out batch (-type) exposure and batch (-type) metallide to obtain this sample.Therefore, gained is netted is 5cm * 5cm size.
By making in this way, can not obtain to comprise as continuously 3m or longer netted electromagnetic shielding film in the present invention.
By method for printing screen, electrolytic copper plating is carried out in the paste of printing containing metal Pd particulate and the cathode copper plating bath of use copper sulphate and formalin in as the net-like pattern among the sample 1-1, thereby obtains comparative sample 1-4.Because use method for printing screen, net-like pattern and silk screen size have same size.What so obtain can the netted of shielding electromagnetic wave be the size of 20cm * 20cm.
Use this comparative sample restricted passage to use the pattern dimension of the electromagnetic shielding film of its preparation.Therefore, can not obtain electromagnetic shielding film greater than the continuous silk screen size of constant pattern wherein.
Embodiment 2
(preparation of filter)
Handle the continuous film of aforesaid sample 1-1 so that copper surface melanism with the copper blackened solution.As blackened solution, use commercially available prod COPPER BLACK (producing) by ISOLATEKAGAKU KENKYUSHO.
The surface resistivity of this electromagnetic shielding film is 0.3 Ω/.
The visible light transmittance rate of this electromagnetic shielding film is 90%.
So the light-transmitting electromagnetic screened film that obtains has electromagnetic wave shielding ability and the near-infrared shielding ability (light transmittance of 800-1000nm ray: 15% or lower) can not cause practical problems.In addition, this film has been realized this two kinds of performances simultaneously with the monofilm form.
Use U-3500 type spectrophotometer (producing) to measure light transmittance by HITACHI.
The gained film has by form metal net shaped of the fine rule of live width 12 μ m and do not cause the part of loss in the preparation filter.
By using aforesaid film, glass plate is adhered to the inside (removing the periphery of 20mm) of light-transmitting electromagnetic screened film by acrylic acid printing opacity contact adhesive (thickness 25 μ m) with light transmittance and electromagnetic wave shielding ability.Acrylic acid printing opacity contact adhesive comprises color correction dyestuff (PS-Red-G, PS-Violet-RC; Produce by MITSUI CHEMICALS) control the light transmission features of filter.By contact adhesive bonding antireflection film (REALOOK on the principal phase opposite of glass plate TMProduce by NOF), thus filter obtained.
So the filter that obtains has the ferrous metal net, in display image, do not have the color metallization, show electromagnetic wave shielding ability and near infrared ray and cut off the ability (light transmittance of 800-1000nm ray: 15% or lower) can not cause practical problems, and because anti-reflection layer and aspect observability, be excellent.In addition, the dyestuff that is added is given the color correction function.Therefore, can be suitably as the filter in the plasma scope etc.
Although the present invention has been described, understands not deviating under the spirit and scope of the present invention with those skilled in the art know that and can carry out variations and modifications with reference to specific embodiments.
The present invention is based on the applying date and be the Japanese patent application (Japanese patent application 2005-073584) on March 15th, 2005 and by reference its content is added this paper.

Claims (13)

1. light-transmitting electromagnetic screened film, it has argent part and light transmission part, and they are formed at the emulsus liquid layer that comprises silver salt emulsion on the support by exposure, and developing then forms, and
Wherein said light-transmitting electromagnetic screened film has infrared shield character.
2. according to the light-transmitting electromagnetic screened film of claim 1, it comprises the infrared ray absorbing dyestuff in support.
3. according to the light-transmitting electromagnetic screened film of claim 1, comprise the infrared ray absorbing dyestuff in its layer on being formed at support.
4. according to the light-transmitting electromagnetic screened film of claim 3, it is dividing being formed in the layer on the support of opposition side to comprise the infrared ray absorbing dyestuff with metallic silver portion.
5. according to the light-transmitting electromagnetic screened film of claim 3, it is comprising the infrared ray absorbing dyestuff with being formed in the layer on the support of metallic silver portion branch same side.
6. according to the light-transmitting electromagnetic screened film of claim 1, it has adhesive layer and comprise the infrared ray absorbing dyestuff in described adhesive layer.
7. according to any one light-transmitting electromagnetic screened film of claim 1-6, it has the conducting metal part that contains conducting metal in argent part, described conducting metal part is by using physical development to described metallic silver portion branch and/or electroplating processes forms.
8. according to the light-transmitting electromagnetic screened film of claim 7,
Wherein said conducting metal part forms by 1 μ m-40 μ m size that netted fine rule is formed and the continuous 3m of described net-like pattern or longer.
9. according to any one light-transmitting electromagnetic screened film of claim 1-8,
Wherein carry out described exposure by the support that when carrying support, has an emulsus liquid layer that comprises silver salt emulsion with the light beam scan exposure.
10. according to any one light-transmitting electromagnetic screened film of claim 1-9,
Wherein the silver-colored netting gear that obtains by the described emulsus liquid layer of developing the surface resistivity of 1-1000 Ω/ is arranged and under the transporting velocity at 1-30m/min after the development treatment by metallide continuously.
11. according to any one light-transmitting electromagnetic screened film of claim 3-10,
The wherein said layer that comprises the layer of infrared ray absorbing dyestuff or contact with the described layer that comprises the infrared ray absorbing dyestuff comprises the antistatic agent that contains inorganic oxide.
12. filter, it comprises any one the light-transmitting electromagnetic screened film according to claim 1-11.
13. plasma display, it comprises any one light-transmitting electromagnetic screened film or the filter according to claim 12 according to claim 1-11.
CNA2006800083192A 2005-03-15 2006-03-14 Light-transmitting electromagnetic shielding film, optical filter and plasma television Pending CN101142868A (en)

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